Water-soluble polyvinyl alcohol blend film, related methods, and related articles

ABSTRACT

Disclosed herein are water-soluble films including a polyvinyl alcohol (PVOH) resin blend and optionally one or more additional components such as plasticizers, fillers, surfactants, and other additives. The PVOH resin blend includes a first copolymer including a first anionic monomer unit and a second PVOH copolymer including a second anionic monomer unit. When the PVOH copolymers are blended in particular proportions and/or selected with regard to various criteria related to physical and chemical film properties, the resulting water-soluble film formed from the PVOH resin blend exhibits maintained film stiffness, and pouch tautness when in contact with liquid pouch contents, and/or maintain acceptable clarity properties, without impairing the ultimate solubility of the water-soluble film.

FIELD OF THE INVENTION

The present disclosure relates generally to water-soluble films andrelated packets. More particularly the disclosure relates to polyvinylalcohol based water-soluble films which include a blend of polyvinylalcohol (PVOH) resins and which can be used for contact with liquids,solids, or combinations thereof with one or more benefits such asmaintaining film stiffness and maintaining pouch tautness when enclosingliquid compositions, such as low molecular weight polyols.

BACKGROUND

Water-soluble polymeric films are commonly used as packaging materialsto simplify dispersing, pouring, dissolving and dosing of a material tobe delivered. For example, pouches made from water-soluble film arecommonly used to package household care compositions such as laundry anddish detergents. A consumer can directly add the pouched composition toa mixing vessel, such as a bucket, sink or washing machine.Advantageously, this provides for accurate dosing while eliminating theneed for the consumer to measure the composition. The pouchedcomposition may also reduce mess that would be associated withdispensing a similar composition from a vessel, such as pouring a liquidlaundry detergent from a bottle. In sum, soluble pre-measured polymericfilm pouches provide for convenience of consumer use in a variety ofapplications.

Some water-soluble polymeric films that are used to make currentlymarketed pouches interact with the pouch components (e.g., detergents),which affects the properties of the pouch, for example the ability tomaintain film stiffness. For example, pouches may demonstrate filmsoftening over time when in contact with contents therein, such asliquid solvents commonly used in liquid detergent compositions, and lowmolecular weight polyols. Such softening can, for example, reduce thetautness of the pouch and impart on the pouch a loose and droopyappearance and feel. In another type of problem, the clarity of the filmmay be affected by a blooming effect of pouch components migratingthrough the film. In another type of problem, the solubility of the filmmay decrease over time when in contact with contents therein, resultingin undesirable residue remaining after a wash. In another type ofproblem, the mechanical properties of the film may change over time whenin contact with the contents therein, resulting in undesirablestiffening of the film or increased brittleness of the film.

Additionally, the COMMISSION REGULATION (EU) No. 1297/2014 of 5 Dec.2014 amended, for the purposes of its adaptation to technical andscientific progress, Regulation (EC) No. 1272/2008 of the EuropeanParliament and of the Council on classification, labeling and packagingof substances and mixtures to require additional provisions for liquidconsumer laundry detergent in dosages for single use contained in asoluble packaging. Among those provisions were the requirements that thesoluble packaging shall retain its liquid content for at least 30seconds when the soluble packaging is placed in water at 20° C.Naturally, the film must thereafter disintegrate and preferablycompletely dissolve, to release the contents of the pouch.

Thus, there exists a need in the art for a water soluble film that iswater soluble and can be formed into packages for holding liquidcompositions, which can be thermoformed or vertical form filled, thatmaintain film stiffness and remain taut, and/or maintain acceptableclarity properties, without impairing the ultimate solubility of thewater-soluble film.

SUMMARY

One aspect of the disclosure provides a water-soluble film including apolyvinyl alcohol (PVOH) resin blend including a first PVOH copolymerincluding a first anionic monomer unit, the first anionic monomer unitselected from the group consisting of alkyl acrylates, alkylalkacrylates, hydrolyzed alkali metal salts of the foregoing, andcombinations of the foregoing, and a second PVOH copolymer including asecond anionic monomer unit, wherein the first anionic monomer unit isdifferent from the second anionic monomer unit and optionally the firstPVOH copolymer is provided in an amount in a range of about 10 wt. % toabout 40 wt. %, based on the total weight of the PVOH resin blend.

Another aspect of the disclosure provides an article comprising thewater-soluble film of the disclosure in the form of a pouch defining aninterior pouch volume, and optionally containing a composition in theinterior pouch volume, e.g. a liquid composition.

Further aspects and advantages will be apparent to those of ordinaryskill in the art from a review of the following detailed description.While the film, pouch, and their methods of making are susceptible ofembodiments in various forms, the description hereafter includesspecific embodiments with the understanding that the disclosure isillustrative, and is not intended to limit the invention to the specificembodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of a wire frame cage (shown with the top open,to better illustrate water-soluble pouches contained therein) for use inthe Liquid Release Test described herein.

FIG. 2 shows an apparatus for performing the Liquid Release Test,including a beaker resting on a stand, the stand holding a rod forlowering a cage into the beaker, the rod being fixable by a collar witha set screw (not shown).

FIGS. 3a and 3b are plots of the DC residue values over time for filmsstored at ambient temperatures (FIG. 3a ) and a 38° C., 80% RHenvironment (FIG. 3b ) for films made of PVOH resin blends including aPVOH-acrylate copolymer and a PVOH-maleate copolymer. The percentPVOH-acrylate copolymer of the blend is indicated in the legend, and thebalance of the resin is the maleate copolymer.

FIGS. 4a and 4b are plots the film dissolution at 10° C. over time forfilms stored at ambient temperatures (FIG. 4a ) and a 38° C., 80% RHenvironment (FIG. 4b ) for films made of PVOH resin blends including aPVOH-acrylate copolymer and a PVOH-maleate copolymer. The percentPVOH-acrylate copolymer of the blend is indicated in the legend, and thebalance of the resin is the maleate copolymer.

DETAILED DESCRIPTION

One aspect of the disclosure provides a water-soluble film including apolyvinyl alcohol (PVOH) resin blend including a first PVOH copolymerincluding a first anionic monomer unit, the first anionic monomer unitselected from the group consisting of alkyl acrylates, alkylalkacrylates, hydrolyzed alkali metal salts of the foregoing, andcombinations of the foregoing and a second PVOH copolymer including asecond anionic monomer unit, wherein the first PVOH copolymer isprovided in an amount in a range of about 10 wt. % to about 40 wt. %,based on the total weight of the PVOH resin blend, and the first anionicmonomer unit is different from the second anionic monomer unit.

In embodiments, the first PVOH copolymer is present in an amount in arange from about 10 wt. % to about 40 wt. % of total weight of the PVOHresin blend. In embodiments, the second PVOH copolymer is present in anamount in a range of from about 60 wt. % to about 90 wt. %, or about 60wt. % to about 80 wt. % of the total weight of the PVOH resin blend.

In embodiments of the disclosure, the first and second PVOH copolymersinclude pendant groups provided by the anionic monomer unit. A pendantgroup, as used herein, includes pendant groups from any monomercopolymerized with a vinyl ester and does not include residual estergroups or hydrolyzed ester groups from the vinyl ester. For example,acetate groups from polymerization of vinyl acetate and hydroxyl groupsformed from hydrolyzing residual acetate groups are not consideredpendant groups. In embodiments, the first PVOH copolymer has a firstlevel of pendant groups (a₁) and the second PVOH copolymer has a secondlevel of pendant groups (a₂), wherein the difference between a₁ and a₂is from about 2 mol % to about 10 mol %. The first pendant group and thesecond pendant group may be together present in a combined amount in arange of about 2 mol % to 15 mol %, or about 2 mol % to 10 mol %. Inembodiments, the first PVOH copolymer is an alkyl acrylate copolymerhaving a first level of anionic monomer incorporation (b₁), the secondPVOH copolymer is a maleic anhydride copolymer having a second level ofanionic monomer incorporation (b₂), wherein the difference between b₁and b₂ is from about 0.2 to 2 mol %. In embodiments, the first PVOHcopolymer has a 4% solution viscosity at 20° C. in a range of about 4 cPto about 24 cP. In embodiments, the second PVOH copolymer has a 4%solution viscosity at 20° C. in a range of about 12 cP to about 30 cP.

In embodiments, the water-soluble film has a residue value of about 35wt. % or less as measured by the Dissolution Chamber Test (“DCResidue”). In embodiments, the water-soluble film can have a swellingratio value, as determined by the Film Swelling Test, that is no greaterthan 60% of the swelling ratio value of a comparative film which isidentical but for the second PVOH copolymer being the sole resin and theamount of that second PVOH copolymer in the comparative film being equalto the total amount of resins in the inventive water-soluble film.

In embodiments, the PVOH resin blend consists essentially of the firstPVOH copolymer and the second PVOH copolymer. In embodiments, thewater-soluble film further comprises at least a third water-solublepolymer which is other than a PVOH polymer. In embodiments, the firstPVOH copolymer and the second PVOH copolymer each independently have adegree of hydrolysis in a range of about 75% to about 99%.

In embodiments, the first PVOH copolymer includes an alkyl acrylatemonomer unit, the first PVOH copolymer is present in an amount in arange from about 10 wt % to about 40 wt % of total weight of the PVOHresin blend, the second PVOH copolymer includes a second anionic monomerunit selected from the group consisting of maleic anhydride, alkalimetal salts thereof, and combinations of the foregoing, the second PVOHcopolymer is present in an amount in a range of about 60 wt % to about90 wt % of total weight of the PVOH resin blend, wherein the differencebetween a₁ and a₂ is from about 2 mol % to about 6 mol %, a₁ is in arange of about 4 mol % to about 6 mol %, a₂ is in a range of about 7 mol% to about 9 mol %, and the first pendant group and the second pendantgroup are together present in a combined amount in a range of about 10mol % to 15 mol %.

In embodiments, the first PVOH copolymer comprises an alkyl acrylatemonomer unit and is present in an amount in a range of from about 10 wt.% to about 40 wt. % of the total weight of the PVOH resin blend, and thewater-soluble film further includes a plasticizer in an amount of atleast 30 PHR.

In embodiments, the first PVOH copolymer comprises an alkyl acrylatemonomer unit and is present in an amount in a range of from about 10 wt.% to about 40 wt. % of the total weight of the PVOH resin blend, and thewater-soluble film further includes a first plasticizer having a molarmass greater than or equal to 92 g/mol and a second plasticizer having amolar mass greater than or equal to 150 g/mol. Optionally, the watersoluble film may further comprise a third plasticizer.

In embodiments, the first PVOH copolymer comprises an alkyl acrylatemonomer unit and is present in an amount in a range of from about 10 wt.% to about 40 wt. % of the total weight of the PVOH resin blend, and thewater-soluble film further includes at least 2 PHR of a filler selectedfrom a bulking agent, an anti-blocking agent, or combinations thereof.

Another aspect of the disclosure provides an article comprising thewater-soluble film of the disclosure in the form of a pouch defining aninterior pouch volume. In embodiments, the article further includes acomposition contained in the interior pouch volume. Optionally, thecomposition contained in the interior pouch volume is a liquidcomposition. Optionally, the liquid composition is a liquid detergent.Optionally, the liquid detergent includes a low molecular weight polyol.Optionally, the composition contained in the interior pouch volume is asolid.

In embodiments, the composition contained in the interior pouch volumeis a liquid and the article has a delayed release time of at least 30seconds as measured by the Liquid Release Test. In embodiments, thecomposition contained in the interior pouch volume is a liquid and thearticle has a compression strength greater than 300 N as measured by theCompression Test Measurement. In embodiments, the composition containedin the interior pouch volume is a liquid and the article has acompression strength less than 2000 N as measured by the CompressionTest Measurement.

“Comprising” as used herein means that various components, ingredientsor steps that can be conjointly employed in practicing the presentdisclosure. Accordingly, the term “comprising” encompasses the morerestrictive terms “consisting essentially of” and “consisting of.” Thepresent compositions can comprise, consist essentially of, or consist ofany of the required and optional elements disclosed herein. For example,a thermoformed packet can “consist essentially of” a film describedherein for use of it thermoforming characteristics, while including anon-thermoformed film (e.g., lid portion), and optional markings on thefilm, e.g. by inkjet printing. The invention illustratively disclosedherein suitably may be practiced in the absence of any element or stepwhich is not specifically disclosed herein.

All percentages, parts and ratios referred to herein are based upon thetotal dry weight of the film composition or total weight of the packetcontent composition of the present disclosure, as the case may be, andall measurements made are at about 25° C., unless otherwise specified.All such weights as they pertain to listed ingredients are based on theactive level and therefore do not include carriers or by-products thatmay be included in commercially available materials, unless otherwisespecified.

All ranges set forth herein include all possible subsets of ranges andany combinations of such subset ranges. By default, ranges are inclusiveof the stated endpoints, unless stated otherwise. Where a range ofvalues is provided, it is understood that each intervening value betweenthe upper and lower limit of that range and any other stated orintervening value in that stated range, is encompassed within thedisclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges, and are alsoencompassed within the disclosure, subject to any specifically excludedlimit in the stated range. Where the stated range includes one or bothof the limits, ranges excluding either or both of those included limitsare also contemplated to be part of the disclosure.

It is expressly contemplated that for any number value described herein,e.g. as a parameter of the subject matter described or part of a rangeassociated with the subject matter described, an alternative which formspart of the description is a functionally equivalent range surroundingthe specific numerical value (e.g. for a dimension disclosed as “40 mm”an alternative embodiment contemplated is “about 40 mm”).

As used herein, the terms packet(s) and pouch(es) should be consideredinterchangeable. In certain embodiments, the terms packet(s) andpouch(es), respectively, are used to refer to a container made using thefilm, and to a fully-sealed container preferably having a materialsealed therein, e.g., in the form a measured dose delivery system. Thesealed pouches can be made from any suitable method, including suchprocesses and features such as heat sealing, solvent welding, andadhesive sealing (e.g., with use of a water-soluble adhesive).

As used herein and unless specified otherwise, the terms “wt. %” and “wt%” are intended to refer to the composition of the identified element in“dry” (non water) parts by weight of the entire film, including residualmoisture in the film (when applicable) or parts by weight of the entirecomposition enclosed within a pouch (when applicable).

As used herein and unless specified otherwise, the term “PHR” (“phr”) isintended to refer to the composition of the identified element in partsper one hundred parts water-soluble polymer resin (whether PVOH or otherpolymer resins, unless specified otherwise) in the water-soluble film,or a solution used to make the film.

The film can be made by any suitable method, including a solutioncasting method. The film can be used to form a container (pouch) by anysuitable process, including vertical form, fill, and sealing (VFFS), orthermoforming. The film can be sealed by any suitable process including,for example, solvent sealing or heat sealing of film layers, e.g. arounda periphery of a container. The pouches can be used for dosing materialsto be delivered into bulk water, for example.

The film, pouches, and related methods of making and use arecontemplated to include embodiments including any combination of one ormore of the additional optional elements, features, and steps furtherdescribed below (including those shown in the Examples and figures),unless stated otherwise.

In any embodiment, the water-soluble pouch can contain (enclose) acomposition. The composition can be selected from a liquid, solid orcombination thereof. As used herein, “liquid” includes free-flowingliquids, as well as pastes, gels, foams and mousses. Non-limitingexamples of liquids include light duty and heavy duty liquid detergentcompositions, fabric enhancers, detergent gels commonly used forlaundry, bleach and laundry additives. Non-limiting examples of liquidsinclude agricultural compositions, automotive compositions, aviationcompositions, food and nutritive compositions, industrial compositions,livestock compositions, marine compositions, medical compositions,mercantile compositions, military and quasi-military compositions,office compositions, and recreational and park compositions, petcompositions, water-treatment compositions, including cleaning anddetergent compositions applicable to any such use. Gases, e.g.,suspended bubbles, or solids, e.g. particles, may be included within theliquids. A “solid” as used herein includes, but is not limited to,powders, agglomerates, and mixtures thereof. Non-limiting examples ofsolids include: granules, micro-capsules, beads, noodles, and pearlisedballs. Solid compositions may provide a technical benefit including, butnot limited to, through-the-wash benefits, pre-treatment benefits,and/or aesthetic effects.

In any of the laundry-centric embodiments, the composition may beselected from the group of liquid light duty and liquid heavy dutyliquid detergent compositions, powdered detergent compositions, fabricenhancers, detergent gels commonly used for laundry, and bleach (e.g.,organic or inorganic bleach) and laundry additives, for example.

Water-Soluble Film

The film and related pouches described herein comprise a water-solublefilm. In one aspect, the water-soluble film comprises a polyvinylalcohol (PVOH) resin blend comprising a first PVOH copolymer comprisinga first anionic monomer unit selected from the group consisting of alkylacrylates, alkyl alkacrylates, hydrolyzed alkali metal salts of theforegoing, and combinations of the foregoing, and a second PVOHcopolymer comprising a second anionic monomer unit. The film can haveany suitable thickness, and a film thickness of about 76 microns (μm) istypical and particularly contemplated. Other values and rangescontemplated include values in a range of about 5 to about 200 μm, or ina range of about 20 to about 100 μm, or about 40 to about 90 μm, orabout 50 to 80 μm, or about or about 60 to 65 μm for example 65 μm, 76μm, or 88 μm.

PVOH Resin

Polyvinyl alcohol is a synthetic resin generally prepared by thealcoholysis, usually termed hydrolysis or saponification, of polyvinylacetate. Fully hydrolyzed PVOH, where virtually all the acetate groupshave been converted to alcohol groups, is a strongly hydrogen-bonded,highly crystalline polymer which dissolves only in hot water—greaterthan about 140° F. (about 60° C.). If a sufficient number of acetategroups are allowed to remain after the hydrolysis of polyvinyl acetate,that is the PVOH polymer is partially hydrolyzed, then the polymer ismore weakly hydrogen-bonded, less crystalline, and is generally solublein cold water—less than about 50° F. (about 10° C.). As such, thepartially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymerthat is a PVOH copolymer, but is commonly referred to as PVOH.

In particular, the PVOH resin will include a partially or fullyhydrolyzed PVOH copolymer that includes an anionic monomer unit, a vinylalcohol monomer unit, and optionally a vinyl acetate monomer unit.

Water-soluble polymeric films based on PVOH can be subject to changes insolubility characteristics. The acetate group in the co-poly(vinylacetate vinyl alcohol) polymer is known by those skilled in the art tobe hydrolysable by either acid or alkaline hydrolysis. As the degree ofhydrolysis increases, a polymer composition made from the PVOHhomopolymer resin will have increased mechanical strength but reducedsolubility at lower temperatures (e.g., requiring hot water temperaturesfor complete dissolution). Accordingly, exposure of a PVOH homopolymerresin to an alkaline environment (e.g., resulting from a laundrybleaching additive) can transform the resin from one which dissolvesrapidly and entirely in a given aqueous environment (e.g., a cold watermedium) to one which dissolves slowly and/or incompletely in the aqueousenvironment, potentially resulting in undissolved polymeric residue atthe end of a wash cycle. This is an inherent weakness in the applicationof films based on just the vinyl acetate/alcohol co-polymer typified bycommercial PVOH homopolymer resins.

PVOH copolymer resins with pendant carboxyl groups, such as, forexample, vinyl alcohol/hydrolyzed methyl acrylate sodium salt resins,can form lactone rings between neighboring pendant carboxyl and alcoholgroups, thus reducing the water solubility of the PVOH copolymer resin.In the presence of a strong base such as a laundry bleaching additive,the lactone rings can open over the course of several weeks atrelatively warm (ambient) and high humidity conditions (e.g., vialactone ring-opening reactions to form the corresponding pendantcarboxyl and alcohol groups with increased water solubility). Thus,contrary to the effect observed with PVOH homopolymer films, it isbelieved that such a PVOH copolymer film can become more soluble due tochemical interactions between the film and an alkaline compositioninside the pouch during storage. Consequently, as they age, the packetsmay become increasingly prone to premature dissolution during a hot washcycle (nominally 40° C.), and may in turn decrease the efficacy ofcertain laundry actives due to the presence of the bleaching agent andthe resulting pH influence.

In formulating a suitable film for a given application (e.g., acomposition-in-pouch article for a washing operation), multiple factorsmust be taken in to account. These factors include: (1) film strength,where a higher strength desirably translates into stronger pouch sealswhen the film is the weak link in a seal; (2) change in film modulusafter exposure to a liquid, where a positive change in modulus desirablyprovides a lower likelihood to soften, loosen, and droop when formulatedinto a pouch encapsulating a liquid composition and/or deform and stickto other films when loaded on top of each other during production or infinal consumer packaging; (3) film swelling ratio value after exposureto a liquid solution, wherein the lower the swelling ratio valuedesirably provides a greater film stiffness, a smaller change in filmarea (length×width) after exposure to the liquid solution, and a greaterpouch tautness and lower likelihood to soften, loosen, and droop whenformulated into a pouch encapsulating a liquid composition; (4)dissolution residue, where a lower residue value desirably lessens thelikelihood of residual film remaining after aggressive washingconditions (e.g., low water (such as in overloading of a washingmachine) and cold wash water conditions); (5) degree and type of anionicmodification, where certain modifications in the polymer desirablyreduce the risk of blooming of pouch components, such as plasticizers,and/or softening of the film when the film is formulated into a pouchencapsulating a composition; and (6) film crystallinity, where a lowercrystallinity value desirably lessens the likelihood of residual filmremaining after aggressive washing conditions and a higher crystallinityvalue desirably lessens the likelihood of softening, loosening, ordrooping when formulated into a pouch encapsulating a liquidcomposition. Often, water-soluble polymer resins, whether PVOH orotherwise, may have suitable characteristics with respect to some ofthese factors, but they can have poor characteristics with respect toother of these factors. Accordingly, it would be desirable to provide awater-soluble film in which many, if not all, of these factors havefavorable properties in the film.

Accounting for these factors, the present disclosure includes awater-soluble film including a polyvinyl alcohol (PVOH) resin blend andoptionally one or more additional components including plasticizers,fillers, surfactants, and other additives as described in more detailbelow. The PVOH resin blend includes a first PVOH resin which is a PVOHcopolymer (“first PVOH copolymer”) including one or more types ofanionic monomer units (e.g., a PVOH ter- (or higher co-) polymer) and asecond PVOH resin which is a PVOH copolymer (“second PVOH copolymer”)including one or more types of anionic monomer units (e.g., a PVOHter-(or higher co-) polymer). In some aspects, the PVOH resin blendincludes only the first PVOH copolymer and the second PVOH copolymer(e.g., a binary blend of the two polymers). Alternatively oradditionally, the PVOH resin blend, the water-soluble film, or both canbe characterized as being free or substantially free from other polymers(e.g., other water-soluble polymers generally, other PVOH-based polymersspecifically, or both). As used herein, “substantially free” means thatthe first and second PVOH copolymers make up at least 95 wt. %, at least97 wt. %, or at least 99 wt. % of the total amount of water-solublepolymers in the water-soluble film. In other aspects, the water-solublefilm can include one or more additional water-soluble polymers. Forexample, the PVOH resin blend can include a third PVOH polymer, a fourthPVOH polymer, a fifth PVOH polymer, etc. (e.g., one or more additionalPVOH homopolymers or PVOH copolymers, with or without anionic monomerunits). For example, the water-soluble film can include at least a third(or fourth, fifth, etc.) water-soluble polymer which is other than aPVOH polymer (e.g., other than PVOH homopolymers or PVOH copolymers,with or without anionic monomer units).

The PVOH copolymer (e.g., the first PVOH copolymer, the second PVOHcopolymer, and any other PVOH copolymers in the resin blend) can be aPVOH terpolymer including vinyl alcohol monomer units, vinyl acetatemonomer units (i.e., when not completely hydrolyzed), and a single typeof anionic monomer unit (e.g., a where a single type of monomer unit caninclude equivalent acid forms, salt forms, and optionally ester forms ofthe anionic monomer unit). In some aspects, the PVOH copolymer caninclude two or more types of anionic monomer units. General classes ofanionic monomer units which can be used for the PVOH copolymer includethe vinyl polymerization units corresponding to monocarboxylic acidvinyl monomers, their esters and anhydrides, dicarboxylic monomershaving a polymerizable double bond, their esters and anhydrides, andalkali metal salts of any of the foregoing. Examples of suitable anionicmonomer units include the vinyl polymerization units corresponding tovinyl anionic monomers including vinyl acetic acid, maleic acid,monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid,monoalkyl fumarate, dialkyl fumarate, fumaric anhydride, itaconic acid,monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, citraconicacid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride,mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconicanhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate,glutaconic anhydride, alkyl acrylates, alkyl alkacrylates, alkali metalsalts of the foregoing, hydrolyzed alkali metal salts of the foregoing,esters of the foregoing, and combinations of the foregoing.

In one type of embodiment, the PVOH is a carboxyl group modifiedcopolymer. In another aspect, the PVOH can be modified with a dicarboxyltype monomer. In one class of these embodiments, the α carbon of bothcarbonyls are connected to the unsaturated bond (e.g., maleic acid,fumaric acid). In another class of these embodiments, the α carbon ofboth carbonyls are connected to the unsaturated bond and the unsaturatedbond is further substituted, e.g., with a methyl branch (e.g.,citraconic acid, mesaconic acid). In another class of these embodiments,the β carbon of one carbonyl and the α carbon of the other carbonyl areconnected to the unsaturated bond (e.g., itaconic acid, cis-glutaconicacid, trans-glutaconic acid). Monomers that provide alkyl carboxylgroups are contemplated. A maleate type (e.g., dialkyl maleate ormonoalkyl maleate, including monomethyl maleate) comonomer isparticularly contemplated.

In embodiments, the first PVOH copolymer includes a first anionicmonomer selected from the group consisting of alkyl acrylates, alkylalkacrylates, hydrolyzed alkali metal salts of the foregoing andcombinations of the foregoing. In embodiments, the second PVOH copolymerincludes a second anionic monomer selected from the group consisting ofmaleic anhydride, alkali metal salts thereof, and combinations of theforegoing.

The level of incorporation of the one or more anionic monomer units inthe PVOH copolymers is not particularly limited. In embodiments, the oneor more anionic monomer units are present in the PVOH copolymer in anamount in a range of about 1 mol. % or 2 mol. % to about 6 mol. % or 10mol. % (e.g., at least 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 mol. %and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mol. % in variousembodiments).

The PVOH copolymers can also be characterized by the level of pendantcarboxyl groups present in the copolymer. PVOH copolymer resins withpendant carboxyl groups can form lactone rings between neighboringpendant carboxyl and alcohol groups. The lactone rings can be opened inthe presence of a caustic agent, as is known in the art. Alactone-containing polymer can be caustically treated such that all ofthe lactone rings are opened or only some of the rings are opened. Forexample, lactone rings form in PVOH-methyl acrylate copolymers and canbe treated such that, for example, 70% of the lactone rings are opened.Accordingly, the level of pendant groups represents the maximum amountof pendant groups that can be present in a copolymer, based on the levelof pendant group incorporation in the copolymer, regardless of whetherthose pendant groups are free or in the form of lactone rings, e.g. withneighboring alcohol groups. The level of pendant groups present in thecopolymer may or may not correspond to the level of incorporation of theanionic monomer units. For example, if methyl acrylate is incorporatedinto the PVOH at a level of 5 mol %, the resulting copolymer has about 5mol % pendant groups, even if only 70% of the lactone rings are opened(i.e., 3.5 mol %). Additionally, if the anionic monomer is adicarboxylate, such as a maleic anhydride salt, acid or an esterthereof, the copolymer includes two pendant units per anionic monomerunit incorporated into the copolymer.

The level of pendant groups in the PVOH copolymers is not particularlylimited. In embodiments, the pendant groups are present in the PVOHcopolymer in an amount in a range of about 1 mol. % or 2 mol. % to about6 mol. % or 10 mol. % (e.g., at least 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0,4.5, or 5.0 mol. % and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0,or 10 mol. % in various embodiments). The PVOH resin blend may have anarithmetic weighted average amount of pendant groups (P) in a range ofabout 2 mol % to about 20 mol %. That is, the first pendant group andthe second pendant group together are present in a combined amount in arange of about 2 mol % to about 20 mol %, about 2 mol % to about 15 mol%, about 5 mol % to about 15 mol %, about 5 mol % to about 10 mol %,about 5 mol % to about 8 mol %, or about 10 mol % to about 15 mol %. Thearithmetic weighted average of the pendant groups P is calculated by theformula P=Σ(W_(i)·P_(i)) wherein W_(i) is the weight percentage of therespective PVOH copolymer and P_(i) is the respective mol % of pendantgroups in the PVOH copolymer.

The water-soluble film can contain at least about 50 wt. %, 55 wt. %, 60wt. %, 65 wt. %, 70 wt. %, 75 wt. %, 80 wt. %, 85 wt. %, or 90 wt. %and/or up to about 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, 95 wt. %, or99 wt. % of the PVOH resin blend. In embodiments, the first PVOHcopolymer is present in the water-soluble film in an amount in a rangeof about 10 wt. % to about 40 wt. % (or about 15 wt. % to about 35 wt.%, or about 20 wt. % to about 30 wt %) of total PVOH polymers and PVOHcopolymers in the film (i.e., relative to the PVOH resin blend weight).For example, the first PVOH copolymer can be present in an amount of atleast 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, or 35 wt. %and/or up to about 25 wt. %, 30 wt. %, 35 wt. %, or 40 wt. % of totalPVOH polymers and PVOH copolymers in the film. In embodiments, theforegoing concentrations of first PVOH copolymer alternatively oradditionally can be relative to total water-soluble polymer content infilm, PVOH or otherwise. Of course, the first water-soluble resin canmake up more than 40 wt. % of the total PVOH polymers and PVOHcopolymers in the film, however, as the amount of first water-solubleresin increases above 40 wt. %, the decrease in the swelling ratio valueis not significant, as demonstrated in the examples, while the residuevalues undesireably increase with increasing amounts of firstwater-soluble resin.

In embodiments, the second PVOH copolymer is present in thewater-soluble film in an amount in a range of about 60 wt. % to about 90wt. % (or about 65 wt. % to about 85 wt. %, or about 70 wt. % to about80 wt. %) of total PVOH polymers and PVOH copolymers in the film (i.e.,relative to the PVOH resin blend weight). For example, the second PVOHcopolymer can be present in an amount of at least 60 wt. %, 65 wt. %, 70wt. %, 75 wt. %, 80 wt. %, or 85 wt. % and/or up to about 70 wt. %, 75wt. %, 80 wt. %, 85 wt. %, or 90 wt. % of total PVOH polymers and PVOHcopolymers in the film. In another aspect, the foregoing concentrationsof second PVOH copolymer alternatively or additionally can be relativeto total water-soluble polymer content in film, PVOH or otherwise.

In an aspect of the water-soluble film, the first PVOH copolymerincludes one or more first anionic monomer units, and the second PVOHcopolymer includes one or more second anionic monomer units. The firstand second anionic monomer units in the two PVOH copolymers can be thesame or different in various embodiments. For reference, the first PVOHcopolymer is denoted as having a first level of pendant groups (a₁) anda first level of incorporation (b₁) of the first anionic monomer unitsand the second PVOH copolymer is denoted as having a second level ofpendant groups (a₂) and a second level of incorporation (b₂) of thesecond anionic monomer units.

In a refinement of this aspect, the first and second PVOH copolymers areselected such that the difference between a₁ and a₂ is in a range ofabout 0.5 mol. % to about 12 mol. % (or about 1 mol. % to about 11 mol.%, about 2 mol. % to about 10 mol. %, about 3 mol. % to 6 mol. %, orabout 2 mol. % to about 6 mol. %), and it more generally can be at least0.5, 1, or 2 mol. % and/or up to about 1, 2, 3, 4, 5, 10, or 12 mol. %.Individually, the level of pendant groups (a₁) for the first PVOHcopolymer can be in a range of about 2 mol. % to about 6 mol. % (orabout 3 mol. % to about 5 mol. %, about 3 mol. % to about 4 mol. %,about 4 mol. % to about 6 mol. %, or about 2 mol. %, about 2.5 mol. %,about 3 mol. %, about 3.5 mol. %, about 4 mol. %, about 4.5 mol. %,about 5 mol. %, about 5.5 mol. %, or about 6 mol. %). Alternatively oradditionally, the level of pendant groups (a₂) for the second anionicmonomer units can be in a range of about 6 mol. % to about 12 mol. % (orabout 6 mol. % to about 10 mol. %, or about 7 mol. % to about 9 mol. %,or about 6 mol. %, about 6.5 mol. %, about 7 mol. %, about 7.5 mol. %,about 8 mol. %, about 8.5 mol. %, about 9 mol. %, about 9.5 mol. %,about 10 mol. %, about 10.5 mol. %, about 11 mol. %, about 11.5 mol. %,or about 12 mol. %).

In embodiments, the first and second PVOH copolymers are selected suchthat the difference between b₁ and b₂ is in a range of about 0.2 mol. %to about 2 mol. % (or about 0.3 mol. % to about 1.5 mol. %, about 0.4mol. % to about 1.5 mol. %, or about 0.5 mol. % to about 1.5 mol %), andit more generally can be at least 0.2, 0.3, 0.4 mol. %, or 0.5 mol %and/or up to about 1.0, 1.5, or 2.0 mol. %. Individually, the level ofincorporation (b₁) for the first anionic monomer units (i.e., the amountof anionic modification of the PVOH copolymer) can be in a range ofabout 3 mol. % to about 8 mol. % (or about 4 mol. % to about 6 mol. %,for example, about 5 mol. %) in the first PVOH copolymer. Alternativelyor additionally, the level of incorporation (b₂) for the second anionicmonomer units (i.e., the amount of anionic modification of the PVOHcopolymer) can be in a range of about 2 mol. % to about 6 mol. % (orabout 3 mol. % to about 5 mol. %, for example, about 4 mol. %) in thesecond PVOH copolymer.

The degree of hydrolysis (DH) of the PVOH homopolymers and PVOHcopolymers included in the water-soluble films of the present disclosurecan be in a range of about 75% to about 99% (e.g., about 79% to about92%, about 88% to 92%, about 86.5% to about 89%, or about 88%, 90% or92% such as for cold-water soluble compositions; about 90% to about 99%,about 92% to about 99%, about 95% to about 99%, about 98%, about 99%, orgreater than 99%). As the degree of hydrolysis is reduced, a film madefrom the resin will have reduced mechanical strength but fastersolubility at temperatures below about 20° C. As the degree ofhydrolysis increases, a film made from the polymer will tend to bemechanically stronger and the thermoformability will tend to decrease.The degree of hydrolysis of the PVOH can be chosen such that thewater-solubility of the polymer is temperature dependent, and thus thesolubility of a film made from the polymer and additional ingredients isalso influenced. In one option the film is cold water-soluble. For aco-poly(vinyl acetate vinyl alcohol) polymer that does not include anyother monomers (e.g., not copolymerized with an anionic monomer) a coldwater-soluble film, soluble in water at a temperature of less than 10°C., can include PVOH with a degree of hydrolysis in a range of about 75%to about 90%, or in a range of about 80% to about 90%, or in a range ofabout 85% to about 90%. In another option the film is hot water-soluble.For a co-poly(vinyl acetate vinyl alcohol) polymer that does not includeany other monomers (e.g., not copolymerized with an anionic monomer) ahot water-soluble film, soluble in water at a temperature of at leastabout 60° C., can include PVOH with a degree of hydrolysis of at leastabout 98%.

The degree of hydrolysis of the resin blend can also be characterized bythe arithmetic weighted, average degree of hydrolysis (H°). For example,H° for a PVOH resin that comprises two or more PVOH polymers iscalculated by the formula H°=Σ(Wi·H_(i)) where W_(i) is the weightpercentage of the respective PVOH polymer and H_(i) is the respectivedegrees of hydrolysis.

The viscosity of a PVOH polymer (μ) is determined by measuring a freshlymade solution using a Brookfield LV type viscometer with UL adapter asdescribed in British Standard EN ISO 15023-2:2006 Annex E BrookfieldTest method. It is international practice to state the viscosity of 4%aqueous polyvinyl alcohol solutions at 20° C. All viscosities specifiedherein in Centipoise (cP) should be understood to refer to the viscosityof 4% aqueous polyvinyl alcohol solution at 20° C., unless specifiedotherwise. Similarly, when a resin is described as having (or nothaving) a particular viscosity, unless specified otherwise, it isintended that the specified viscosity is the average viscosity for theresin, which inherently has a corresponding molecular weightdistribution.

For reference, the first PVOH copolymer is denoted as having a first 4%solution viscosity at 20° C. (μ₁), and the second PVOH copolymer isdenoted as having a second 4% solution viscosity at 20° C. (μ₂). Invarious embodiments, the first viscosity μ₁ can be in a range of about 4cP to about 30 cP (e.g., at least about 4, 8, 10, 12, or 16 cP and/or upto about 12, 16, 20, 24, or 30 cP, such as about 4 cP to about 24 cP,about 10 cP to about 16 cP, or about 10 cP to about 20 cP, or about 20cP to about 30 cP). Alternatively or additionally, the second viscosityμ₂ can be in a range of about 4 cP to about 30 cP (e.g., at least about4, 8, 10, 12, or 16 cP and/or up to about 12, 16, 20, 24, or 30 cP, suchas about 12 cP to about 30 cP, about 10 cP to about 16 cP, or about 10cP to about 20 cP, or about 20 cP to about 30 cP). When the PVOH resinblend includes three or more PVOH resins selected from PVOH polymer andPVOH copolymer resins, the foregoing viscosity values can apply to eachPVOH polymer or PVOH copolymer individually. It is well known in the artthat the viscosity of PVOH resins is correlated with the weight averagemolecular weight (Mw) of the PVOH resin, and often the viscosity is usedas a proxy for the Mw. Thus, the weight-average molecular weight of thewater-soluble polymers, including the first PVOH copolymer and thesecond PVOH copolymer, can be in a range of about 30,000 to about175,000, or about 30,000 to about 100,000, or about 55,000 to about80,000, for example. When referring to average viscosity of the PVOHresin blend, the weighted natural log average viscosity (μ) is used. Theμ for a PVOH resin that comprises two or more PVOH polymers iscalculated by the formula μ=e^(ΣW) ^(i) ^(·ln μ) ^(i) where μ_(i) is theviscosity for the respective PVOH polymers.

In another aspect of the water-soluble film, the first PVOH copolymerand the second PVOH copolymer are selected for the PVOH resin blend suchthat the resulting water-soluble film has maintained film stiffness andmaintained pouch tautness (e.g., is less likely to loosen and droop)when in contact with liquid pouch contents, and preferably maintained orimproved dissolution, residue, and mechanical properties as well. Insome embodiments, the water-soluble film has the property in which (a)the water-soluble film has a residue value of about 35 wt. % or less,about 40 wt. % or less, about 45 wt. % or less, or about 48 wt. % orless (e.g., in a range of about 12 wt. % to about 48 wt. %, about 25 wt.% to about 48 wt. %, about 10 wt. % to about 45 wt. %, about 20 wt. % toabout 45 wt. %, or about 25 wt. % to about 40 wt. %) as measured by theDissolution Chamber Test (described below). In some embodiments, thewater-soluble film has the property in which (b) the water-soluble filmhas a crystallinity value of at least 15% (e.g., in a range of about 15%to about 50%, about 15% to about 40%, about 15% to about 35%, about 15%to about 30%, about 15% to about 25%, or about 15% to about 20%) asmeasured by the Crystallinity Test (described below). In someembodiments, the water soluble film has the property in which (c) thewater-soluble film is resistant to the blooming effect as determined byvisual inspection of the opacity of the film of the pouch materialrelative to the opacity of the film when made. In some embodiments, thewater-soluble film has the property in which (d) the water soluble filmhas a swelling ratio value that is no greater than 60% of the swellingratio value of a comparative film which is identical but for the secondPVOH copolymer being the sole resin and the amount of that second PVOHcopolymer in the comparative film being equal to the total amount ofresins in the inventive water-soluble film, as determined by the FilmSwelling Test (described below). It will be appreciated that not each ofproperties (a) through (d) need to be satisfied to provide awater-soluble film having maintained film stiffness and maintained pouchtautness (e.g., is less likely to loosen and droop) when in contact withliquid pouch contents, and preferably maintained or improveddissolution, residue, and mechanical properties. For example, awater-soluble film having a crystallinity value of less than 15% thatdemonstrates maintained film stiffness and maintained pouch tautness canbe designed, for example, by modifying the type and/or amount ofplasticizer provided in the film. In various embodiments, thewater-soluble film has the properties (a) and (b), (a) and (c), (a) and(d), (b) and (c), (b) and (d), (c) and (d), (a) and (b) and (c), (a) and(b) and (d), (a) and (c) and (d), (b) and (c) and (d), or (a) and (b)and (c) and (d). In general, water-soluble films that exhibit theaforementioned properties, exhibit the properties prior to exposure to aliquid composition (e.g. liquid laundry detergent) and maintain theaforementioned properties after exposure to a liquid composition. Thewater-soluble films of the disclosure “maintain” a property afterexposure to a liquid composition if the property has a value afterexposure to a liquid composition that is within the ranges disclosedherein for said property. The water-soluble films of the disclosure neednot maintain the exact same value for a property after exposure to aliquid composition that the film exhibited prior to exposure to a liquidcomposition. For example, in one type of embodiment the property afterexposure can be within 20%, or within 10% of the original value andstill within the range disclosed herein for the property.

The PVOH resin blends according to the disclosure unexpectedly permitthe formulation of water-soluble films having a combination of desirablephysical and chemical properties, even when the PVOH copolymers includedin the resin blends are deficient individually with respect to one ormore of physical or chemical properties. For example, each PVOHcopolymer in the blend has at least one undesirable trait for aparticular property, but the water-soluble film incorporating the blendachieves a desirable trait for the particular property of each PVOHcopolymer. For example, the PVOH resin blend can include first andsecond PVOH copolymers such that a corresponding first PVOH copolymerwater-soluble film has the property (a) and a corresponding second PVOHcopolymer water-soluble film does not have the property (a).Alternatively or additionally, the PVOH resin blend can include firstand second PVOH copolymers such that a corresponding first PVOHcopolymer water-soluble film does not have the property (b); and acorresponding second PVOH copolymer water-soluble film has the property(b). Alternatively or additionally, the PVOH resin blend can includefirst and second PVOH copolymers such that a corresponding first PVOHcopolymer water-soluble film does not have the property (c); and acorresponding second PVOH copolymer water-soluble film has the property(c). Alternatively or additionally, the PVOH resin blend can includefirst and second PVOH copolymers such that a corresponding first PVOHcopolymer water-soluble film does not have the property (d); and acorresponding second PVOH copolymer water-soluble film has the property(d). A corresponding PVOH copolymer denotes a water-soluble filmcontaining only the first PVOH copolymer or the second PVOH copolymer asthe water-soluble polymer resin, but otherwise including the same typeand amounts of plasticizers and other additives, having the samethickness, etc.

Other Water Soluble Polymers

Other water soluble polymers for use in addition to the first and secondPVOH copolymers can include, but are not limited to a vinylalcohol-vinyl acetate copolymer, sometimes referred to as a PVOHhomopolymer, polyacrylates, water-soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, pullulan, water-soluble natural polymersincluding, but not limited to, guar gum, gum Acacia, xanthan gum,carrageenan, and starch, water-soluble polymer derivatives including,but not limited to, modified starches, ethoxylated starch, andhydroxypropylated starch, copolymers of the forgoing and combinations ofany of the foregoing. Yet other water-soluble polymers can includepolyalkylene oxides, polyacrylamides, polyacrylic acids and saltsthereof, celluloses, cellulose ethers, cellulose esters, celluloseamides, polyvinyl acetates, polycarboxylic acids and salts thereof,polyaminoacids, polyamides, gelatines, methylcelluloses,carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses,hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,polymethacrylates, and combinations of any of the foregoing. Suchwater-soluble polymers, whether PVOH or otherwise are commerciallyavailable from a variety of sources.

In embodiments, the PVOH resin blend consists essentially of the firstPVOH copolymer and the second PVOH copolymer. In embodiments, thewater-soluble film comprises at least a third water-soluble polymerwhich is other than a PVOH polymer.

The water-soluble film can contain other auxiliary agents and processingagents, such as, but not limited to, plasticizers, plasticizercompatibilizers, surfactants, lubricants, release agents, fillers,extenders, cross-linking agents, antiblocking agents, antioxidants,detackifying agents, antifoams, nanoparticles such as layeredsilicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents(e.g., sodium metabisulfite, sodium bisulfite or others), aversiveagents such as bitterants (e.g., denatonium salts such as denatoniumbenzoate, denatonium saccharide, and denatonium chloride; sucroseoctaacetate; quinine; flavonoids such as quercetin and naringen; andquassinoids such as quassin and brucine) and pungents (e.g., capsaicin,piperine, allyl isothiocyanate, and resinferatoxin), and otherfunctional ingredients, in amounts suitable for their intended purposes.Embodiments including plasticizers are preferred. The amount of suchagents can be up to about 50 wt. %, 20 wt %, 15 wt %, 10 wt %, 5 wt. %,4 wt % and/or at least 0.01 wt. %, 0.1 wt %, 1 wt %, or 5 wt %,individually or collectively.

Plasticizers

A plasticizer is a liquid, solid, or semi-solid that is added to amaterial (usually a resin or elastomer) making that material softer,more flexible (by decreasing the glass-transition temperature of thepolymer), and easier to process. A polymer can alternatively beinternally plasticized by chemically modifying the polymer or monomer.In addition or in the alternative, a polymer can be externallyplasticized by the addition of a suitable plasticizing agent. Water isrecognized as a very efficient plasticizer for PVOH and other polymers;including but not limited to water soluble polymers, however, thevolatility of water makes its utility limited since polymer films needto have at least some resistance (robustness) to a variety of ambientconditions including low and high relative humidity.

The plasticizer can include, but is not limited to, glycerin,diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethyleneglycol, dipropylene glycol, tetraethylene glycol, propylene glycol,polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane,polyether polyols, sorbitol, 2-methyl-1,3-propanediol (MPDiol®),ethanolamines, and a mixture thereof. A preferred plasticizer isglycerin, sorbitol, triethyleneglycol, propylene glycol, dipropyleneglycol, 2-methyl-1,3-propanediol, trimethylolpropane, or a combinationthereof. The total amount of the non-water plasticizer can be in a rangeof about 10 wt. % to about 40 wt. %, or about 15 wt. % to about 35 wt.%, or about 20 wt. % to about 30 wt. %, for example about 25 wt. %,based on total film weight. Combinations of glycerin, dipropyleneglycol, and sorbitol can be used. Optionally, glycerin can be used in anamount of about 5 wt % to about 30 wt %, or 5 wt % to about 20 wt %,e.g., about 13 wt %. Optionally, dipropylene glycol can be used in anamount of about 1 wt. % to about 20 wt. %, or about 3 wt. % to about 10wt. %, for example 6 wt. %. Optionally, sorbitol can be used in anamount of about 1 wt % to about 20 wt %, or about 2 wt % to about 10 wt%, e.g., about 5 wt %. The specific amounts of plasticizers can beselected in a particular embodiment based on desired film flexibilityand processability features of the water-soluble film. At lowplasticizer levels, films may become brittle, difficult to process, orprone to breaking. At elevated plasticizer levels, films may be toosoft, weak, or difficult to process for a desired use.

In some embodiments the plasticizer can include glycerin, sorbitol, andtrimethyloyl propane. Optionally, the plasticizer can be included in anamount greater than or equal to 30 phr, or greater than 40 phr, forexample in a range of about 30 phr to about 75 phr, about 30 phr toabout 70 phr, about 30 phr to about 60 phr, about 30 phr to about 50phr, or about 30 phr to about 45 phr.

In some embodiments, the plasticizer can include glycerin, sorbitol, and2-methyl-1,3-propanediol. Optionally the plasticizer can be included inan amount less than 30 phr or less than 25 phr, for example in a rangeof about 5 phr to about 30 phr, about 10 phr to about 30 phr, about 15phr to about 30 phr, about 5 phr to about 29 phr, about 5 phr to about25 phr, about 10 phr to about 25 phr, or about 15 phr to about 25 phr.

In some embodiments, the plasticizer can include a first plasticizerhaving a molecular weight of 92 g/mol or greater and a secondplasticizer having a molecular weight of 150 g/mol or greater. Forexample, the first plasticizer can have a molecular weight in a range ofabout 92 g/mol to about 149 g/mol, about 92 g/mol to about 140 g/mol,about 92 g/mol to about 130 g/mol, about 92 g/mol to about 120 g/mol,about 92 g/mol to about 110 g/mol, or about 92 g/mol to about 100 g/mol,and the second plasticizer can have a molecular weight in a range ofabout 150 g/mol to 200 g/mol, for example, about 150 g/mol to about 190g/mol, about 160 g/mol to about 190 g/mol, about 170 g/mol to about 190g/mol, or about 180 g/mol to about 190 g/mol.

It will be understood that individual plasticizers can be characterizedby Hansen Solubility Parameters that are outside a defined Hansen area,but that by blending plasticizers the resulting combination or ratio canthen fall within the defined Hansen area. Accordingly, when more thanone plasticizer is used for the polymer resin, the combination will beselected such that it is characterized by the Hansen SolubilityParameters described herein.

The solubility characteristics of a material can be characterized bythree individual forces: dispersive forces (δ_(D)), polar forces(δ_(P)), and hydrogen bonding forces (δ_(H)). The individual forces canbe combined into a total cohesive energy value (δ_(T)) as shown inEquation 1:

(δ_(T))²=(δ_(D))²+(δ_(P))²+(δ_(H))².  (1)

In addition to representative solubility parameters for a singlecomponent, a Hansen area can be defined in Hansen Space as a sphere withthe individual solubility parameters (δ_(D)), (δ_(P)), and (δ_(H)) asthe center and a radius RAD defining the extent of the sphere.

In another aspect, the Hansen area definition can further include “Core”values. The core values define how much the center of the sphere(defined by δ_(D), δ_(P), δ_(H), and RAD) can, in a sense, move in theδ_(D), δ_(P), and δ_(H) directions (+ or −) to extend the Hansen area.Thus, the larger the Core values, the less tightly the Hansen areaapproximates a truly spherical area.

Calculations for evaluating the various HSP values can be performedusing a commercially available software package such as HSPIP (availablefrom the Hansen Solubility Parameters internet site, currently in the4^(th) edition). Experimentally good plasticizers and poor plasticizerscan be tested, and the HSP coordinates δ_(D), δ_(P), and δ_(H) for amaterial can be experimentally determined. Alternatively, the individualHSP coordinates δ_(D), δ_(P), and δ_(H) can be computed using the Y-MBmethodology (included in the HSPIP software). Regardless of the methodselected for HSP parameter estimation, a consistent method is suitablyused for all plasticizers and polymeric components of interest.

For example, HSP parameters for common plasticizers are provided in thetable below.

Name Plas δD δP δH Propylene Glycol PG 16.8 10.4 21.3 2 Methyl PropaneDiol 2M-1,3PD 17.1 9.4 20.7 Diethylene Glycol DEG 16.6 12 19Trimethylolpropane TMP 17.1 9.9 21.1 diglycerin DG 17.4 11.9 26.6Dipropylene Glycol DPG 16.5 10.6 17.7 Triethylene Glycol TEG 16 12.518.6 Glycerol GLY 17.4 11.3 27.2 Polyethylene Glycol 200 PEG200 16.4 9.415.3

Surfactants

Surfactants for use in water-soluble films are well known in the art.Optionally, surfactants are included to aid in the dispersion of theresin solution upon casting. Suitable surfactants for water-solublefilms of the present disclosure include, but are not limited to, dialkylsulfosuccinates, lactylated fatty acid esters of glycerol and propyleneglycol, lactylic esters of fatty acids, sodium alkyl sulfates,polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, alkylpolyethylene glycol ethers, lecithin, acetylated fatty acid esters ofglycerol and propylene glycol, sodium lauryl sulfate, acetylated estersof fatty acids, myristyl dimethylamine oxide, trimethyl tallow alkylammonium chloride, quaternary ammonium compounds, alkali metal salts ofhigher fatty acids containing about 8 to 24 carbon atoms, alkylsulfates, alkyl polyethoxylate sulfates, alkylbenzene sulfonates,monoethanolamine, lauryl alcohol ethoxylate, propylene glycol,diethylene glycol, salts thereof and combinations of any of theforgoing.

Suitable surfactants can include the nonionic, cationic, anionic andzwitterionic classes. Suitable surfactants include, but are not limitedto, propylene glycols, diethylene glycols, monoethanolamine,polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides(nonionics), polyoxyethylenated amines, quaternary ammonium salts andquaternized polyoxyethylenated amines (cationics), alkali metal salts ofhigher fatty acids containing about 8 to 24 carbon atoms, alkylsulfates, alkyl polyethoxylate sulfates and alkylbenzene sulfonates(anionics), and amine oxides, N-alkylbetaines and sulfobetaines(zwitterionics). Other suitable surfactants include dioctyl sodiumsulfosuccinate, lactylated fatty acid esters of glycerin and propyleneglycol, lactylic esters of fatty acids, sodium alkyl sulfates,polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80,lecithin, acetylated fatty acid esters of glycerin and propylene glycol,and acetylated esters of fatty acids, and combinations thereof. Invarious embodiments, the amount of surfactant in the water-soluble filmis in a range of about 0.1 wt % to 2.5 wt %, optionally about 1.0 wt %to 2.0 wt %. In embodiments, the amount of surfactant in thewater-soluble film is expressed in parts per 100 parts total watersoluble polymer (phr) in the water-soluble film and is present in arange of about 0.5 phr to about 4 phr, about 0.75 phr to about 3.0 phr,about 1.0 phr to about 2.5 phr, about 1.0 phr to about 2.0 phr, or about1.5 phr.

Surfactants can be characterized in terms of hydrophilic/lipophilicbalance (HLB). Griffin's method was described in 1954 (Griffin W C:“Calculation of HLB Values of Non-Ionic Surfactants,” Journal of theSociety of Cosmetic Chemists 5 (1954): 259) and is used in the art fordetermining HLB values for non-ionic surfactants as follows:HLB=20*Mh/M, where Mh is the molecular mass of the hydrophilic portionof the molecule, and M is the molecular mass of the whole molecule,giving an HLB value on a scale of 0 to 20. An HLB value of 0 correspondsto a completely lipophilic/hydrophobic molecule and a value of 20corresponds to a completely hydrophilic/lipophobic molecule.

Blends of surfactants have been found to be advantageous forwater-soluble films comprising anionic monomers selected from the groupconsisting of maleic acid, maleic anhydride, monoalkyl maleates, dialkylmaleates and combinations thereof. Thus, in an aspect of the disclosure,the second PVOH copolymer comprises an anionic monomer selected from thegroup consisting of maleic acid, maleic anhydride, monoalkyl maleates,dialkyl maleates and combinations thereof, and the water-soluble filmfurther comprises a non-ionic surfactant, an amine oxide surfactant, ananionic surfactant, a cationic surfactant, or a combinations thereof. Inrefinements of the foregoing aspect, the non-ionic surfactant isselected from the group consisting of polyoxyethylenatedpolyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates,tertiary acetylenic glycols, alkanolamides, and combinations thereof. Inrefinements, the amine oxide surfactant is selected from the groupconsisting of dimethyloctylamine oxide, dimethyldecylamine oxide,dimethyldodecylamine oxide, dimethyltetradecylamine oxide,dimethylhexadecylamine oxide, dimethyloctadecylamine oxide andcombinations of the foregoing. It will be appreciated that commerciallyavailable amine oxide surfactants may be blends of the foregoing as thesource of the amines can include a distribution of amines of variouschain length. Accordingly, as an example, in some embodiments a“dimethyldodecylamine oxide,” can include a distribution of amine oxideswherein the average amine oxide and/or the major fraction of amine oxidecomprises a dodecyl chain. In refinements, the anionic surfactant cancomprises dioctyl sodium sulfosuccinate. In refinements, the cationicsurfactant can be selected from the group consisting ofpolyoxyethylenated amines, quaternary ammonium salts, quaternizedpolyoxyethylenated amines, and combinations thereof. In embodiments, thetotal amount of combined surfactants in the water-soluble film is in arange of about 0.5 phr to about 4 phr, about 0.75 phr to about 3.0 phr,about 1.0 phr to about 2.5 phr, about 1.0 phr to about 2.0 phr, or about1.5 phr.

In refinements of the foregoing aspect, each of the surfactants presentin the water-soluble film can be present in an amount in a range ofabout 1 wt. % to about 98 wt. % of the total amount of surfactants, orabout 10 wt. % to about 80 wt. %, or about 15 wt. % to about 70 wt. %,or about 16 wt. % to about 68 wt. %, or about 17 wt. % to about 42 wt.%, or about 30 wt. % to about 40 wt. %.

Suitable lubricants/release agents can include, but are not limited to,fatty acids and their salts, fatty alcohols, fatty esters, fatty amines,fatty amine acetates and fatty amides. Preferred lubricants/releaseagents are fatty acids, fatty acid salts, and fatty amine acetates. Inone type of embodiment, the amount of lubricant/release agent in thewater-soluble film is in a range of about 0.02 wt % to about 1.5 wt %,optionally about 0.1 wt % to about 1 wt %.

Fillers can be included in the water-soluble films and can includebulking agents, extenders, antiblocking agents, detackifying agents andcombinations thereof. Suitable fillers/bulkingagents/extenders/antiblocking agents/detackifying agents include, butare not limited to, starches, modified starches, crosslinkedpolyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose,silica, metallic oxides, calcium carbonate, talc, mica, stearic acid andmetal salts thereof, for example, magnesium stearate. Preferredmaterials are starches, modified starches and silica. In one type ofembodiment, the amount of filler/extender/antiblockingagent/detackifying agent in the water soluble film can be in a range ofabout 1 wt. % to about 6 wt. %, or about 1 wt. % to about 4 wt. %, orabout 2 wt. % to about 4 wt. %, or about 1 phr to about 6 phr, or about1 phr to about 4 phr, or about 2 phr to about 4 phr, for example.

In some embodiments, the water-soluble film can include 2 or more phr(e.g., 2 phr to 6 phr or 2 phr to 4 phr) of a filler. In someembodiments, the film includes 2 or more phr (e.g., 2 phr to 6 phr or 2phr to 4 phr) of a filler and the filler comprises a bulking agent, anantiblocking agent, or a combination thereof. Without intending to bebound by theory, it is believed that the inclusion of 2 or more phr(e.g., 2 phr to 6 phr or 2 phr to 4 phr) of a filler can be useful toprevent weeping or migration of plasticizer out of the film, when theplasticizer is included in an amount of greater than or equal to 30 phr,for example, in a range of 30 phr to 50 phr.

An anti-block agent (e.g. SiO₂ and/or stearic acid)) can be present inthe film in an amount of at least 0.1 PHR, or at least 0.5 PHR, or atleast 1 PHR, or in a range of about 0.1 to 5.0 PHR, or about 0.1 toabout 3.0 PHR, or about 0.4 to 1.0 PHR, or about 0.5 to about 0.9 PHR,or about 0.5 to about 2 PHR, or about 0.5 to about 1.5 PHR, or 0.1 to1.2 PHR, or 0.1 to 2.7 PHR, for example 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8PHR, or 0.9 PHR.

A suitable median particle size for the anti-block agent includes amedian size in a range of about 3 to about 11 microns, or about 4microns to about 11 microns, or about 4 to about 8 microns, or about 5to about 6 microns, for example 5, 6, 7, 8, or 9 microns. A suitableSiO₂ is an untreated synthetic amorphous silica designed for use inaqueous systems.

The water-soluble film can further have a residual moisture content ofat least 4 wt. %, for example in a range of about 4 to about 10 wt. %,as measured by Karl Fischer titration.

To be considered a water-soluble film according to the presentdisclosure, the film, at a thickness of about 1.5 mil (about 0.038 mm),dissolves in 300 seconds or less in water at a temperature of 20° C.(68° F.) in accordance with MonoSol Test Method MSTM-205.

Method of Making Film

One contemplated class of embodiments is characterized by thewater-soluble film being formed by solvent casting. Processes forsolvent casting of PVOH are well-known in the art. For example, in thefilm-forming process, the polyvinyl alcohol polymers and secondaryadditives are dissolved in a solvent, typically water, metered onto asurface, allowed to substantially dry (or force-dried) to form a castfilm, and then the resulting cast film is removed from the castingsurface. The process can be performed batchwise, and is more efficientlyperformed in a continuous process.

In the formation of continuous films of polyvinyl alcohol, it is theconventional practice to meter a solution of the solution onto a movingcasting surface, for example, a continuously moving metal drum or belt,causing the solvent to be substantially removed from the liquid, wherebya self-supporting cast film is formed, and then stripping the resultingcast film from the casting surface.

Optionally, the water-soluble film can be a free-standing filmconsisting of one layer or a plurality of like layers.

Pouches

The film disclosed herein is useful for creating pouches to contain acomposition therein. The pouch composition may take any form such aspowders, gels, pastes, liquids, tablets or any combination thereof. Thefilm is also useful for any other application in which improved wethandling and low cold water residues are desired. The film forms atleast one side wall of the pouch, optionally the entire pouch, andpreferably an outer surface of the at least one sidewall.

The film described herein can also be used to make a packet with two ormore compartments made of the same film or in combination with films ofother polymeric materials. Additional films can, for example, beobtained by casting, blow-molding, extrusion or blown extrusion of thesame or a different polymeric material, as known in the art. In one typeof embodiment, the polymers, copolymers or derivatives thereof suitablefor use as the additional film are selected from polyvinyl alcohols,polyvinyl pyrrolidone, polyalkylene oxides, polyacrylic acid, cellulose,cellulose ethers, cellulose esters, cellulose amides, polyvinylacetates, polycarboxylic acids and salts, polyaminoacids or peptides,polyamides, polyacrylamide, copolymers of maleic/acrylic acids,polysaccharides including starch and gelatin, natural gums such asxanthan, and carrageenans. For example, polymers can be selected frompolyacrylates and water-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and combinations thereof, or selected from polyvinylalcohols, polyvinyl alcohol copolymers and hydroxypropyl methylcellulose (HPMC), and combinations thereof. One contemplated class ofembodiments is characterized by the level of polymer in the packetmaterial, for example the PVOH copolymer described above, as describedabove, being at least 60 wt. %, and up to 99 wt. %.

The pouches of the present disclosure can include at least one sealedcompartment. Thus, the pouches may comprise a single compartment ormultiple compartments. A water-soluble pouch can be formed from twolayers of water-soluble polymer film sealed at an interface, or by asingle film that is folded upon itself and sealed. One or both of thefilms include the PVOH film described above. The films define aninterior pouch container volume which contains any desired compositionfor release into an aqueous environment. The composition is notparticularly limited, for example including any of the variety ofcompositions described below. In embodiments comprising multiplecompartments, each compartment may contain identical and/or differentcompositions. In turn, the compositions may take any suitable formincluding, but not limited to liquid, solid and combinations thereof(e.g. a solid suspended in a liquid). In embodiments, the pouchescomprises a first, second and third compartment, each of whichrespectively contains a different first, second, and third composition.

The compartments of multi-compartment pouches may be of the same ordifferent size(s) and/or volume(s). The compartments of the presentmulti-compartment pouches can be separate or conjoined in any suitablemanner. In embodiments, the second and/or third and/or subsequentcompartments are superimposed on the first compartment. In oneembodiment, the third compartment may be superimposed on the secondcompartment, which is in turn superimposed on the first compartment in asandwich configuration. Alternatively the second and third compartmentsmay be superimposed on the first compartment. However it is also equallyenvisaged that the first, second and optionally third and subsequentcompartments may be attached to one another in a side by siderelationship. The compartments may be packed in a string, eachcompartment being individually separable by a perforation line. Henceeach compartment may be individually torn-off from the remainder of thestring by the end-user, for example, so as to pre-treat or post-treat afabric with a composition from a compartment. In embodiments, the firstcompartment may be surrounded by at least the second compartment, forexample in a tire-and-rim configuration, or in a pouch-in-a-pouchconfiguration.

In embodiments, multi-compartment pouches comprise three compartmentsconsisting of a large first compartment and two smaller compartments.The second and third smaller compartments are superimposed on the firstlarger compartment. The size and geometry of the compartments are chosensuch that this arrangement is achievable. The geometry of thecompartments may be the same or different. In embodiments the second andoptionally third compartment each has a different geometry and shape ascompared to the first compartment. In these embodiments, the second andoptionally third compartments are arranged in a design on the firstcompartment. The design may be decorative, educative, or illustrative,for example to illustrate a concept or instruction, and/or used toindicate origin of the product. In embodiments, the first compartment isthe largest compartment having two large faces sealed around theperimeter, and the second compartment is smaller covering less thanabout 75%, or less than about 50% of the surface area of one face of thefirst compartment. In embodiments in which there is a third compartment,the aforementioned structure may be the same but the second and thirdcompartments cover less than about 60%, or less than about 50%, or lessthan about 45% of the surface area of one face of the first compartment.

The pouches of the present disclosure may comprise one or more differentfilms. For example, in single compartment embodiments, the packet may bemade from one wall that is folded onto itself and sealed at the edges,or alternatively, two walls that are sealed together at the edges. Inmultiple compartment embodiments, the packet may be made from one ormore films such that any given packet compartment may comprise wallsmade from a single film or multiple films having differing compositions.In one embodiment, a multi-compartment pouch comprises at least threewalls: an outer upper wall; an outer lower wall; and a partitioningwall. The outer upper wall and the outer lower wall are generallyopposing and form the exterior of the pouch. The partitioning wall isinterior to the pouch and is secured to the generally opposing outerwalls along a seal line. The partitioning wall separates the interior ofthe multi-compartment pouch into at least a first compartment and asecond compartment.

Pouches and packets may be made using any suitable equipment and method.For example, single compartment pouches may be made using vertical formfilling, horizontal form filling, or rotary drum filling techniquescommonly known in the art. Such processes may be either continuous orintermittent. The film may be dampened, and/or heated to increase themalleability thereof. The method may also involve the use of a vacuum todraw the film into a suitable mold. The vacuum drawing the film into themold can be applied for about 0.2 to about 5 seconds, or about 0.3 toabout 3, or about 0.5 to about 1.5 seconds, once the film is on thehorizontal portion of the surface. This vacuum can be such that itprovides an under-pressure in a range of 10 mbar to 1000 mbar, or in arange of 100 mbar to 600 mbar, for example.

The molds, in which packets may be made, can have any shape, length,width and depth, depending on the required dimensions of the pouches.The molds may also vary in size and shape from one to another, ifdesirable. For example, the volume of the final pouches may be about 5ml to about 300 ml, or about 10 to 150 ml, or about 20 to about 100 ml,and that the mold sizes are adjusted accordingly.

In one embodiment, the packet comprises a first and a second sealedcompartment. The second compartment is in a generally superposedrelationship with the first sealed compartment such that the secondsealed compartment and the first sealed compartment share a partitioningwall interior to the pouch.

In one embodiment, the packet comprising a first and a secondcompartment further comprises a third sealed compartment. The thirdsealed compartment is in a generally superposed relationship with thefirst sealed compartment such that the third sealed compartment and thefirst sealed compartment share a partitioning wall interior to thepouch.

In embodiments, the first composition and the second composition areselected from one of the following combinations: liquid, liquid; liquid,powder; powder, powder; and powder, liquid.

In some embodiments, the first, second and third compositions areselected from one of the following combinations: solid, liquid, liquidand liquid, liquid, liquid.

In one embodiment, the single compartment or plurality of sealedcompartments contains a composition. The plurality of compartments mayeach contain the same or a different composition. The composition isselected from a liquid, solid or combination thereof.

In one embodiment, the composition may be selected from the group ofliquid light duty and liquid heavy duty liquid detergent compositions,powdered detergent compositions, dish detergent for hand washing and/ormachine washing; hard surface cleaning compositions, fabric enhancers,detergent gels commonly used for laundry, and bleach and laundryadditives, shampoos, and body washes, agricultural compositions,automotive compositions, aviation compositions, food and nutritivecompositions, industrial compositions, livestock compositions, marinecompositions, medical compositions, mercantile compositions, militaryand quasi-military compositions, office compositions, and recreationaland park compositions, pet compositions, water-treatment compositions,including cleaning and detergent compositions applicable to any suchuse.

Vertical Form, Fill, and Sealing

One conventional automated process includes a vertical form, fill, andseal (VFFS) process. VFFS includes an apparatus such as an assemblymachine that wraps a single piece of the film around a verticallyoriented feed tube. The machine heat seals or otherwise secures theopposing edges of the film together to create the side seal and form ahollow tube of film. Subsequently, the machine heat seals or otherwisecreates the bottom seal, thereby defining a container portion with anopen top where the top seal will later be formed. The machine introducesa specified amount of flowable product into the container portionthrough the open top end. Once the container includes the desired amountof product, the machine advances the film to another heat sealingdevice, for example, to create the top seal. Finally, the machineadvances the film to a cutter that cuts the film immediately above thetop seal to provide a filled package.

During operation, the assembly machine advances the film from a roll toform the package. Accordingly, the film must be able to readily advancethrough the machine and not adhere to the machine assembly or be sobrittle as to break during processing.

Shaping, Sealing, and Thermoforming

A thermoformable film is one that can be shaped through the applicationof heat and a force. In general, the films of the disclosure arethermoformable.

As is known in the art, thermoforming a film is the process of heatingthe film, shaping it (e.g. in a mold), and then allowing the film tocool, whereupon the film will hold its shape, e.g. the shape of themold. The heat may be applied using any suitable means. For example, thefilm may be heated directly by passing it under a heating element orthrough hot air, prior to feeding it onto a surface or once on asurface. Alternatively, it may be heated indirectly, for example byheating the surface or applying a hot item onto the film. Inembodiments, the film is heated using an infrared light. The film may beheated to a temperature in a range of about 50 to about 150° C., about50 to about 120° C., about 60 to about 130° C., about 70 to about 120°C., or about 60 to about 90° C. Thermoforming can be performed by anyone or more of the following processes: the manual draping of athermally softened film over a mold, or the pressure induced shaping ofa softened film to a mold (e.g., vacuum forming), or the automatichigh-speed indexing of a freshly extruded sheet having an accuratelyknown temperature into a forming and trimming station, or the automaticplacement, plug and/or pneumatic stretching and pressuring forming of afilm.

Alternatively, the film can be wetted by any suitable means, for exampledirectly by spraying a wetting agent (including water, a solution of thefilm composition, a plasticizer for the film composition, or anycombination of the foregoing) onto the film, prior to feeding it ontothe surface or once on the surface, or indirectly by wetting the surfaceor by applying a wet item onto the film.

Once a film has been heated and/or wetted, it may be drawn into anappropriate mold, preferably using a vacuum. The filling of the moldedfilm can be accomplished by utilizing any suitable means. Inembodiments, the most preferred method will depend on the product formand required speed of filling. In embodiments, the molded film is filledby in-line filling techniques. The filled, open packets are then closedforming the pouches, using a second film, by any suitable method. Thismay be accomplished while in horizontal position and in continuous,constant motion. The closing may be accomplished by continuously feedinga second film, preferably water-soluble film, over and onto the openpackets and then preferably sealing the first and second film together,typically in the area between the molds and thus between the packets.

Any suitable method of sealing the packet and/or the individualcompartments thereof may be utilized. Non-limiting examples of suchmeans include heat sealing, solvent welding, solvent or wet sealing, andcombinations thereof. Typically, only the area which is to form the sealis treated with heat or solvent. The heat or solvent can be applied byany method, typically on the closing material, and typically only on theareas which are to form the seal. If solvent or wet sealing or weldingis used, it may be preferred that heat is also applied. Preferred wet orsolvent sealing/welding methods include selectively applying solventonto the area between the molds, or on the closing material, by forexample, spraying or printing this onto these areas, and then applyingpressure onto these areas, to form the seal. Sealing rolls and belts asdescribed above (optionally also providing heat) can be used, forexample.

The formed pouches may then be cut by a cutting device. Cutting can beaccomplished using any suitable method. It may be preferred that thecutting is also done in continuous manner, and preferably with constantspeed and preferably while in horizontal position. The cutting devicecan, for example, be a sharp item, or a hot item, or a laser, whereby inthe latter cases, the hot item or laser ‘burns’ through the film/sealingarea.

The different compartments of a multi-compartment pouches may be madetogether in a side-by-side style wherein the resulting, cojoined pouchesmay or may not be separated by cutting. Alternatively, the compartmentscan be made separately.

In embodiments, pouches may be made according to a process comprisingthe steps of: a) forming a first compartment (as described above); b)forming a recess within or all of the closed compartment formed in step(a), to generate a second molded compartment superposed above the firstcompartment; c) filling and closing the second compartments by means ofa third film; d) sealing the first, second and third films; and e)cutting the films to produce a multi-compartment pouch. The recessformed in step (b) may be achieved by applying a vacuum to thecompartment prepared in step (a).

In embodiments, second, and/or third compartment(s) can be made in aseparate step and then combined with the first compartment as describedin U.S. Patent Application Publication No. 2014/345064 A1 or U.S. PatentApplication Publication No. 2009/312220 A1.

In embodiments, pouches may be made according to a process comprisingthe steps of: a) forming a first compartment, optionally using heatand/or vacuum, using a first film on a first forming machine; b) fillingthe first compartment with a first composition; c) on a second formingmachine, deforming a second film, optionally using heat and vacuum, tomake a second and optionally third molded compartment; d) filling thesecond and optionally third compartments; e) sealing the second andoptionally third compartment using a third film; f) placing the sealedsecond and optionally third compartments onto the first compartment; g)sealing the first, second and optionally third compartments; and h)cutting the films to produce a multi-compartment pouch.

The first and second forming machines may be selected based on theirsuitability to perform the above process. In embodiments, the firstforming machine is preferably a horizontal forming machine, and thesecond forming machine is preferably a rotary drum forming machine,preferably located above the first forming machine.

It should be understood that by the use of appropriate feed stations, itmay be possible to manufacture multi-compartment pouches incorporating anumber of different or distinctive compositions and/or different ordistinctive liquid, gel or paste compositions.

In embodiments, the film and/or pouch is sprayed or dusted with asuitable material, such as an active agent, a lubricant, an aversiveagent, or mixtures thereof. In embodiments, the film and/or pouch isprinted upon, for example, with an ink and/or an active agent.

Pouch Contents

The present articles (e.g., in the form of pouches or packets) maycontain various compositions, for example household care compositions. Amulti-compartment pouch may contain the same or different compositionsin each separate compartment. The composition is proximal to thewater-soluble film. The composition may be less than about 10 cm, orless than about 5 cm, or less than about 1 cm from the film. Typicallythe composition is adjacent to the film or in contact with the film. Thefilm may be in the form of a pouch or a compartment, containing thecomposition therein.

This feature of the disclosure may be utilized to keep compositionscontaining incompatible ingredients (e.g., bleach and enzymes)physically separated or partitioned from each other. It is believed thatsuch partitioning may expand the useful life and/or decrease physicalinstability of such ingredients. Additionally or alternatively, suchpartitioning may provide aesthetic benefits as described in U.S. Pat.No. 8,835,372.

A fabric or household care composition includes fabric treatments, hardsurfaces, air care, car care, dishwashing, fabric conditioning andsoftening, laundry detergency, laundry and rinse additive and/or care,hard surface cleaning and/or treatment, and other cleaning for consumeror institutional use. Non-household care compositions are for otheruses.

Non-limiting examples of useful compositions (e.g., household carecompositions) include light duty and heavy duty liquid detergentcompositions, hard surface cleaning compositions, detergent gelscommonly used for laundry, bleach and laundry additives, fabric enhancercompositions (such as fabric softeners), shampoos, body washes, andother personal care compositions. Compositions of use in the presentpouches may take the form of a liquid, solid or a powder. Liquidcompositions may comprise a solid. Solids may include powder oragglomerates, such as micro-capsules, beads, noodles or one or morepearlized balls or mixtures thereof. Such a solid element may provide atechnical benefit, through the wash or as a pre-treat, delayed orsequential release component; additionally or alternatively, it mayprovide an aesthetic effect.

Non-limiting examples of other useful compositions (e.g., non-householdcare compositions) include agricultural compositions, aviationcompositions, food and nutritive compositions, industrial compositions,livestock compositions, marine compositions, medical compositions,mercantile compositions, military and quasi-military compositions,office compositions, and recreational and park compositions, petcompositions, water-treatment compositions, including cleaning anddetergent compositions applicable to any such use while excluding fabricand household care compositions. Compositions of use in the presentpouches may take the form of a liquid, solid or a powder. Liquidcompositions may comprise a solid. Solids may include powder oragglomerates, such as micro-capsules, beads, noodles or one or morepearlized balls or mixtures thereof. Such a solid element may provide atechnical benefit, through the wash or as a pre-treat, delayed orsequential release component; additionally or alternatively, it mayprovide an aesthetic effect.

The compositions encapsulated by the films described herein can have anysuitable viscosity depending on factors such as formulated ingredientsand purpose of the composition. In one embodiment, the composition has ahigh shear viscosity value, at a shear rate of 20 s⁻¹ and a temperatureof 20° C., of 100 to 3,000 cP, alternatively 300 to 2,000 cP,alternatively 500 to 1,000 cP, and a low shear viscosity value, at ashear rate of 1 s⁻¹ and a temperature of 20° C., of 500 to 100,000 cP,alternatively 1000 to 10,000 cP, alternatively 1,300 to 5,000 cP.Methods to measure viscosity are known in the art. According to thepresent disclosure, shear viscosity measurements of compositions otherthan PVOH polymer solutions are carried out using a rotational rheometere.g. TA instruments AR550. The instrument includes a 40 mm 2° or 1° conefixture with a gap of around 50-60 μm for isotropic liquids, or a 40 mmflat steel plate with a gap of 1000 μm for particles containing liquids.The measurement is carried out using a flow procedure that contains aconditioning step, a peak hold and a continuous ramp step. Theconditioning step involves the setting of the measurement temperature at20° C., a pre-shear of 10 seconds at a shear rate of 10 s⁻¹, and anequilibration of 60 seconds at the selected temperature. The peak holdinvolves applying a shear rate of 0.05 s⁻¹ at 20° C. for 3 min withsampling every 10 s. The continuous ramp step is performed at a shearrate from 0.1 to 1200 s⁻¹ for 3 min at 20° C. to obtain the full flowprofile.

As described above, the composition may be a non-household carecomposition. For example, a non-household care composition can beselected from agricultural compositions, aviation compositions, food andnutritive compositions, industrial compositions, livestock compositions,marine compositions, medical compositions, mercantile compositions,military and quasi-military compositions, office compositions, andrecreational and park compositions, pet compositions, water-treatmentcompositions, including cleaning and detergent compositions applicableto any such use while excluding fabric and household care compositions

In one type of embodiment, the composition can include an agrochemical,e.g. one or more insecticides, fungicides, herbicides, pesticides,miticides, repellants, attractants, defoliaments, plant growthregulators, fertilizers, bactericides, micronutrients, and traceelements. Suitable agrochemicals and secondary agents are described inU.S. Pat. Nos. 6,204,223 and 4,681,228 and EP 0989803 A1. For example,suitable herbicides include paraquat salts (for example paraquatdichloride or paraquat bis(methylsulphate), diquat salts (for examplediquat dibromide or diquat alginate), and glyphosate or a salt or esterthereof (such as glyphosate isopropylammonium, glyphosate sesquisodiumor glyphosate trimesium, also known as sulfosate). Incompatible pairs ofcrop protection chemicals can be used in separate chambers, for exampleas described in U.S. Pat. No. 5,558,228. Incompatible pairs of cropprotection chemicals that can be used include, for example, bensulfuronmethyl and molinate; 2,4-D and thifensulfuron methyl; 2,4-D and methyl2-[[[[N-4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate;2,4-D and metsulfuron methyl; maneb or mancozeb and benomyl; glyphosateand metsulfuron methyl; tralomethrin and any organophosphate such asmonocrotophos or dimethoate; bromoxynil andN-[[4,6-dimethoxypyrimidine-2-yl)-amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine-sulfonamide;bromoxynil and methyl2-[[[[(4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-benzoate;bromoxynil and methyl2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate.In another, related, type of embodiment, the composition can include oneor more seeds, optionally together with soil, and further optionallytogether with one or more additional components selected from mulch,sand, peat moss, water jelly crystals, and fertilizers, e.g. includingtypes of embodiments described in U.S. Pat. No. 8,333,033.

In another type of embodiment, the composition is a water-treatmentagent. Such agents include aggressive oxidizing chemicals, e.g. asdescribed in U.S. Patent Application Publication No. 2014/0110301 andU.S. Pat. No. 8,728,593. For example, sanitizing agents can includehypochlorite salts such as sodium hypochlorite, calcium hypochlorite,and lithium hypochlorite; chlorinated isocyanurates such asdichloroisocyanuric acid (also referred to as “dichlor” ordichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinane-2,4,6-trione)and trichloroisocyanuric acid (also referred to as “trichlor” or1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione). Salts and hydrates ofthe sanitizing compounds are also contemplated. For example,dichloroisocyanuric acid may be provided as sodium dichloroisocyanurate,sodium dichloroisocyanurate acid dihydrate, among others. Brominecontaining sanitizing agents may also be suitable for use in unit dosepackaging applications, such as 1,3-dibromo-5,5-dimethylhydantoin(DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyano aceticacid amide, 1-bromo-3-chloro-5,5-dimethylhydantoin; and2-bromo-2-nitro-1,3-propanediol, among others. The oxidizing agent canbe one described in U.S. Pat. No. 7,476,325, e.g. potassium hydrogenperoxymonosulfate. The composition can be a pH-adjusting chemical, e.g.as described in U.S. Patent Application Publication No. 2008/0185347,and can include, for example, an acidic component and an alkalinecomponent such that the composition is effervescent when contacted withwater, and adjusts the water pH. Suitable ingredients include sodiumbicarbonate, sodium bisulfate, potassium hydroxide, sulfamic acid,organic carboxylic acids, sulfonic acids, and potassium dihydrogenphosphate. A buffer blend can include boric acid, sodium carbonate,glycolic acid, and oxone monopersulfate, for example.

A water-treatment agent can be or can include a flocculant, e.g. asdescribed in U.S. Patent Application Publication No. 2014/0124454. Theflocculant can include a polymer flocculant, e.g. polyacrylamide, apolyacrylamide copolymer such as an acrylamide copolymers ofdiallydimethylammonium chloride (DADMAC), dimethylaminoethylacrylate(DMAEA), dimethylaminoethylmethacrylate (DMAEM),3-methylamidepropyltrimethylammonium chloride (MAPTAC) or acrylic acid;a cationic polyacrylamide; an anionic polyacrylamide; a neutralpolyacrylamide; a polyamine; polyvinylamine; polyethylene imine;polydimethyldiallylammonium chloride; poly oxyethylene; polyvinylalcohol; polyvinyl pyrrolidone; polyacrylic acid; polyphosphoric acid;polystyrene sulfonic acid; or any combination thereof. A flocculant canbe selected from chitosan acetate, chitosan lactate, chitosan adipate,chitosan glutamate, chitosan succinate, chitosan malate, chitosancitrate, chitosan fumarate, chitosan hydrochloride, and combinationsthereof. The water-treating composition can include a phosphate removingsubstance, e.g. one or more selected from a zirconium compound, a rareearth lanthanide salt, an aluminum compound, an iron compound, or anycombination thereof.

The composition can be a limescale removing composition, e.g. citric ormaleic acid or a sulphate salt thereof, or any mixture thereof, e.g. asdescribed in U.S. Patent Application No. 2006/0172910.

Various other types of compositions are contemplated for use in thepackets described herein, including particulates, for example downfeathers, e.g. as described in U.S. RE29059 E; super absorbent polymers,e.g. as described in U.S. Patent Application Publication Nos.2004/0144682 and 2006/0173430; pigments and tinters, e.g. as describedin U.S. Pat. No. 3,580,390 and U.S. Patent Application Publication No.2011/0054111; brazing flux (e.g. alkali metal fluoroaluminates, alkalimetal fluorosilicates and alkali metal fluorozincates), e.g. asdescribed in U.S. Pat. No. 8,163,104; food items (e.g., coffee powder ordried soup) as described in U.S. Patent Application Publication No.2007/0003719; and wound dressings, e.g. as described in U.S. Pat. No.4,466,431.

In pouches comprising laundry, laundry additive and/or fabric enhancercompositions, the compositions may comprise one or more of the followingnon-limiting list of ingredients: fabric care benefit agent; detersiveenzyme; deposition aid; rheology modifier; builder; bleach; bleachingagent; bleach precursor; bleach booster; bleach catalyst; perfume and/orperfume microcapsules (see for example U.S. Pat. No. 5,137,646); perfumeloaded zeolite; starch encapsulated accord; polyglycerol esters;whitening agent; pearlescent agent; enzyme stabilizing systems;scavenging agents including fixing agents for anionic dyes, complexingagents for anionic surfactants, and mixtures thereof; opticalbrighteners or fluorescers; polymer including but not limited to soilrelease polymer and/or soil suspension polymer; dispersants; antifoamagents; non-aqueous solvent; fatty acid; suds suppressors, e.g.,silicone suds suppressors (see: U.S. Publication No. 2003/0060390 A1,¶65-77); cationic starches (see: US 2004/0204337 A1 and US 2007/0219111A1); scum dispersants (see: US 2003/0126282 A1, ¶89-90); substantivedyes; hueing dyes (see: US 2014/0162929 A1); colorants; opacifier;antioxidant; hydrotropes such as toluenesulfonates, cumenesulfonates andnaphthalenesulfonates; color speckles; colored beads, spheres orextrudates; clay softening agents; anti-bacterial agents. Any one ormore of these ingredients is further described in described in U.S.Patent Application Publication Number US 2010/305020 A1, U.S.Publication Number 2003/0139312 A1 and U.S. Patent ApplicationPublication Number US 2011/0023240 A1. Additionally or alternatively,the compositions may comprise surfactants, quaternary ammoniumcompounds, and/or solvent systems. Quaternary ammonium compounds may bepresent in fabric enhancer compositions, such as fabric softeners, andcomprise quaternary ammonium cations that are positively chargedpolyatomic ions of the structure NR₄ ⁺, where R is an alkyl group or anaryl group.

Surfactants

The detergent compositions can comprise from about 1% to 80% by weightof a surfactant. Surfactant is particularly preferred as a component ofthe first composition. Preferably, the first composition comprises fromabout 5% to 50% by weight of surfactant. The second and thirdcompositions may comprise surfactant at levels of from 0.1 to 99.9%.

Detersive surfactants utilized can be of the anionic, nonionic,zwitterionic, ampholytic or cationic type or can comprise compatiblemixtures of these types. More preferably surfactants are selected fromthe group consisting of anionic, nonionic, cationic surfactants andmixtures thereof. Preferably the compositions are substantially free ofbetaine surfactants. Detergent surfactants useful herein are describedin U.S. Pat. Nos. 3,664,961; 3,919,678; 4,222,905; and 4,239,659.Anionic and nonionic surfactants are preferred.

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkyl ammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoap.

Additional non-soap anionic surfactants which are suitable for useherein include the water-soluble salts, preferably the alkali metal, andammonium salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 10 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester group. (Includedin the term “alkyl” is the alkyl portion of acyl groups.) Examples ofthis group of synthetic surfactants include: a) the sodium, potassiumand ammonium alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈-C₁₈) such as those produced by reducing theglycerides of tallow or coconut oil; b) the sodium, potassium andammonium alkyl polyethoxylate sulfates, particularly those in which thealkyl group contains from 10 to 22, preferably from 12 to 18 carbonatoms, and wherein the polyethoxylate chain contains from 1 to 15,preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassiumalkylbenzene sulfonates in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 13, abbreviated as C₁₁-C₁₃ LAS.

Preferred nonionic surfactants are those of the formula R₁(OC₂H₄)_(n)OH,wherein R₁ is a C₁₀-C₁₆ alkyl group or a C₈-C₁₂ alkyl phenyl group, andn is from 3 to about 80. Particularly preferred are condensationproducts of C₁₂-C₁₅ alcohols with from about 5 to about 20 moles ofethylene oxide per mole of alcohol, e.g., C₁₂-C₁₃ alcohol condensed withabout 6.5 moles of ethylene oxide per mole of alcohol.

Solvent System

The solvent system in the detergent compositions can be a solvent systemcontaining water alone or mixtures of organic solvents with water.Preferred organic solvents include 1,2-propanediol, ethanol, glycerin,dipropylene glycol, methyl propane diol and mixtures thereof. Otherlower alcohols, low molecular weight polyols, C₁-C₄ alkanolamines suchas monoethanolamine and triethanolamine, can also be used. As usedherein a “low molecular weight polyol” is a molecule with more than twohydroxyl groups that has a molecular weight in a range of 50 g/mol and1000 g/mol, 50 g/mol to 800 g/mol, or 50 g/mol to 600 g/mol. Solventsystems can be absent, for example from anhydrous solid detergentembodiments of the disclosure, but more typically are present at levelsin the range of from about 0.1% to about 98%, preferably at least about1% to about 50%, more usually from about 5% to about 25% by weight.Typically, the present detergent compositions, particularly when inliquid form, comprise less than 50% water, preferably from about 0.1% toabout 20% water, or more preferably from about 0.5% to about 15%, orfrom about 3% to about 12%, by weight of the composition, of water.Typically, the present detergent compositions, particularly when inliquid form, comprise from about 5% to about 20% or from about 10% toabout 15% glycerin, by weight of the composition. Typically, the presentdetergent compositions, particularly when in liquid form, comprise lessthan 30% propylene glycol, for example, from about 0.1% to 25% propyleneglycol, 0.5% to 20% propylene glycol, or 5% to 15% propylene glycol, byweight of the composition.

The detergent compositions herein can generally be prepared by mixingthe ingredients together. If a pearlescent material is used it should beadded in the late stages of mixing. If a rheology modifier is used, itis preferred to first form a pre-mix within which the rheology modifieris dispersed in a portion of the water and optionally other ingredientseventually used to comprise the detergent compositions. This pre-mix isformed in such a way that it forms a structured liquid. To thisstructured pre-mix can then be added, while the pre-mix is underagitation, the surfactant(s) and essential laundry adjunct materials,along with water and whatever optional detergent composition adjunctsare to be used.

The pH of the detergent compositions may be from about 2 to about 12,about 4 to about 12, about 5.5 to about 9.5, about 6 to about 8.5, orabout 6.5 to about 8.2. Laundry detergent compositions may have a pH ofabout 6 to about 10, about 6.5 to about 8.5, about 7 to about 7.5, orabout 8 to about 10. Auto-dishwashing compositions may have a pH ofabout 8 to about 12. Laundry detergent additive compositions may have apH of about 4 to about 8. Fabric enhancers may have a pH of from about 2or 4 to about 8, or from about 2 to about 4, or from about 2.5 to about3.5, or from about 2.7 to about 3.3.

The pH of the detergent is defined as the pH of an aqueous 10%(weight/volume) solution of the detergent at 20° C.±2° C.; for solidsand powdered detergent this is defined as the pH of an aqueous 1%(weight/volume) solution of the detergent at 20° C.±2° C. Any metercapable of measuring pH to ±0.01 pH units is suitable. Orion meters(Thermo Scientific, Clintinpark-Keppekouter, Ninovesteenweg 198, 9320Erembodegem-Aalst, Belgium) or equivalent are acceptable instruments.The pH meter should be equipped with a suitable glass electrode withcalomel or silver/silver chloride reference. An example includes MettlerDB 115. The electrode shall be stored in the manufacturer's recommendedelectrolyte solution.

The 10% aqueous solution of the detergent is prepared according to thefollowing procedure. A sample of 10±0.05 grams is weighted with abalance capable of accurately measuring to ±0.02 grams. The sample istransferred to a 100 mL volumetric flask, diluted to volume withpurified water (deionized and/or distilled water are suitable as long asthe conductivity of the water is <50/cm), and thoroughly mixed. About 50mL of the resulting solution is poured into a beaker, the temperature isadjusted to 20° C.±2° C. and the pH is measured according to thestandard procedure of the pH meter manufacturer (it is critical tofollow the manufacturer's instructions to also set up and calibrate thepH assembly).

For solid and powdered detergents, the 1% aqueous solution of thedetergent is prepared according to the following procedure. A sample of10±0.05 grams is weighted with a balance capable of accurately measuringto ±0.02 grams. The sample is transferred to a volumetric flask of 1000mL, diluted to volume with purified water (deionized and/or distilledwater are suitable as long as the conductivity of the water is <50/cm),and thoroughly mixed. About 50 mL of the resulting solution is pouredinto a beaker, the temperature is adjusted to 20° C.±2° C. and the pH ismeasured according to the standard procedure of the pH metermanufacturer (it is critical to follow the manufacturer's instructionsto also set up and calibrate the pH assembly).

It is known in the art that, when formed into a pouch enclosing acomposition, some film components (e.g., plasticizers) can, in somecircumstances, migrate from the film into the enclosed composition and,additionally or alternatively, some components of the enclosedcomposition (e.g., plasticizer, solvent) can migrate into the film.Without intending to be bound by theory, it is believed that thismigration of components into/out of the film can result in changes tothe films swelling value.

Bleaches

Inorganic and organic bleaches are suitable cleaning actives for useherein. Inorganic bleaches include perhydrate salts such as perborate,percarbonate, perphosphate, persulfate and persilicate salts. Theinorganic perhydrate salts are normally the alkali metal salts. Theinorganic perhydrate salt may be included as the crystalline solidwithout additional protection. Alternatively, the salt can be coated asis known in the art.

Alkali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates for use in the detergent composition describedherein. The percarbonate is most preferably incorporated into theproducts in a coated form and/or encapsulated, which provides in-productstability. A suitable coating material providing in product stabilitycomprises mixed salt of a water-soluble alkali metal sulphate andcarbonate. Such coatings together with coating processes have previouslybeen described in GB 1,466,799, and U.S. Pat. Nos. 3,975,280; 4,075,116;and 5,340,496, each incorporated herein by reference. The weight ratioof the mixed salt coating material to percarbonate lies in the rangefrom 1:99 to 1:9, and preferably from 1:49 to 1:19. Preferably, themixed salt is of sodium sulphate and sodium carbonate which has thegeneral formula Na₂SO₄.n.Na₂CO₃ wherein n is from 0.1 to 3, preferablyfrom 0.3 to 1.0, and more preferably from 0.2 to 0.5. Another suitablecoating material providing in product stability comprises sodiumsilicate of SiO₂: Na₂O ratio from 1.8:1 to 3.0:1, preferably 1.8:1 to2.4:1, and/or sodium metasilicate, preferably applied at a level of from2% to 10%, (normally from 3% to 5%) of SiO₂ by weight of the inorganicperhydrate salt, such as potassium peroxymonopersulfate. Other coatingswhich contain magnesium silicate, silicate and borate salts, silicateand boric acids, waxes, oils, and fatty soaps can also be usedadvantageously

Organic bleaches can include organic peroxyacids including diacyl andtetraacylperoxides, especially diperoxydodecanedioc acid,diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoylperoxide is a preferred organic peroxyacid herein. The diacyl peroxide,especially dibenzoyl peroxide, preferably can be present in the form ofparticles having a weight average diameter of from about 0.1 to about100 microns, preferably from about 0.5 to about 30 microns, morepreferably from about 1 to about 10 microns. Preferably, at least about25% to 100%, more preferably at least about 50%, even more preferably atleast about 75%, most preferably at least about 90%, of the particlesare smaller than 10 microns, preferably smaller than 6 microns.

Other organic bleaches include the peroxy acids, particular examplesbeing the alkylperoxy acids and the arylperoxy acids. Preferredrepresentatives are: (a) peroxybenzoic acid and its ring-substitutedderivatives, such as alkylperoxybenzoic acids, but alsoperoxy-α-naphthoic acid and magnesium monoperphthalate; (b) thealiphatic or substituted aliphatic peroxy acids, such as peroxylauricacid, peroxystearic acid, ε-phthalimidoperoxycaproicacid[phthaloiminoperoxyhexanoic acid (PAP)],o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid andN-nonenylamidopersuccinates; and (c) aliphatic and araliphaticperoxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid,1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid,the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid,N,N-terephthaloyldi(6-aminopercaproic acid)

Bleach activators can include organic peracid precursors that enhancethe bleaching action in the course of cleaning at temperatures of 60° C.and below. Bleach activators suitable for use herein include compoundswhich, under perhydrolysis conditions, give aliphatic peroxoycarboxylicacids having preferably from 1 to 10 carbon atoms, in particular from 2to 4 carbon atoms, and/or optionally substituted perbenzoic acid.Suitable substances bear O-acyl and/or N-acyl groups of the number ofcarbon atoms specified and/or optionally substituted benzoyl groups.Preference is given to polyacylated alkylenediamines, in particulartetraacetylethylenediamine (TAED), acylated triazine derivatives, inparticular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated glycolurils, in particular tetraacetylglycoluril (TAGU),N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylatedphenolsulfonates, in particular n-nonanoyl- orisononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,in particular phthalic anhydride, acylated polyhydric alcohols, inparticular triacetin, ethylene glycol diacetate and2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC).

Bleach catalysts preferred for use in the detergent composition hereininclude the manganese triazacyclononane and related complexes (U.S. Pat.Nos. 4,246,612 and 5,227,084); Co, Cu, Mn and Fe bispyridylamine andrelated complexes (U.S. Pat. No. 5,114,611); and pentamine acetatecobalt(III) and related complexes (U.S. Pat. No. 4,810,410). A completedescription of bleach catalysts suitable for use herein can be found inU.S. Pat. No. 6,599,871, incorporated herein by reference.

Dishwashing Agents

A preferred surfactant for use in automatic dishwashing detergents islow foaming by itself or in combination with other components (e.g. sudssuppressers). Preferred for use herein are low and high cloud pointnonionic surfactants and mixtures thereof including nonionic alkoxylatedsurfactants (especially ethoxylates derived from C₆-C₁₈ primaryalcohols), ethoxylated-propoxylated alcohols (e.g., Olin Corporation'sPOLY-TERGENT® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's POLY-TERGENT® SLF18B—see WO-A-94/22800), ether-cappedpoly(oxyalkylated) alcohol surfactants, and blockpolyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®,REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp.,Wyandotte, Mich.; amphoteric surfactants such as the C₁₂-C₂₀ alkyl amineoxides (preferred amine oxides for use herein include lauryldimethylamine oxide and hexadecyl dimethyl amine oxide), and alkylamphocarboxylic surfactants such as MIRANOL™ C2M; and zwitterionicsurfactants such as the betaines and sultaines; and mixtures thereof.Surfactants suitable for use herein are disclosed, for example, in U.S.Pat. Nos. 3,929,678 and 4,259,217, EP Patent Publication 0414549A1, andPCT patent application publications WO 1994/007974 A1 and WO 1994/007986A1. Surfactants can be present in the detergent at a level of from about0.2% to about 30% by weight, more preferably from about 0.5% to about10% by weight, most preferably from about 1% to about 5% by weight of adetergent composition.

Other Compositions and Additives

Builders suitable for use in the detergent composition described hereininclude water-soluble builders, including citrates, carbonates, silicateand polyphosphates, e.g. sodium tripolyphosphate and sodiumtripolyphosphate hexahydrate, potassium tripolyphosphate and mixedsodium and potassium tripolyphosphate salts.

Enzymes suitable for use in the detergent composition described hereininclude bacterial and fungal cellulases including CAREZYME and CELLUZYME(Novo Nordisk A/S); peroxidases; lipases including AMANO-P (AmanoPharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASEand LIPOLASE ULTRA (Novo); cutinases; proteases including ESPERASE,ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASEand MAXAPEM (Gist-Brocades); a and 13 amylases including PURAFECT OX AM(Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL, and NATALASE (Novo);pectinases; and mixtures thereof. Enzymes can be added herein as prills,granulates, or cogranulates at levels typically in the range from about0.0001% to about 2% pure enzyme by weight of the cleaning composition.

Suds suppressers suitable for use in the detergent composition describedherein include nonionic surfactants having a low cloud point. “Cloudpoint” as used herein, is a well-known property of nonionic surfactantswhich is the result of the surfactant becoming less soluble withincreasing temperature, the temperature at which the appearance of asecond phase is observable is referred to as the “cloud point.” As usedherein, a “low cloud point” nonionic surfactant is defined as a nonionicsurfactant system ingredient having a cloud point of less than 30° C.,preferably less than about 20° C., and even more preferably less thanabout 10° C., and most preferably less than about 7.5° C. Low cloudpoint nonionic surfactants can include nonionic alkoxylated surfactants,especially ethoxylates derived from primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic surfactants caninclude, for example, ethoxylated-propoxylated alcohol (e.g., BASFPOLY-TERGENT SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g.,BASF POLY-TERGENT SLF18B series of nonionics, as described, for example,in U.S. Pat. No. 5,576,281).

Other suitable components for use in the detergent composition describedherein include cleaning polymers having anti-redeposition, soil releaseor other detergency properties. Anti-redeposition polymers for useherein include acrylic acid containing polymers such as SOKALAN PA30,PA20, PA15, PA10 and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N(Rohm and Haas), acrylic acid/maleic acid copolymers such as SOKALAN CP5and acrylic/methacrylic copolymers. Other suitable polymers includeamine-based polymers such as alkoxylated polyalkyleneimines (e.g.,PEI600 EO20 and/or ethoxysulfated hexamethylene diamine dimethyl quats).Soil release polymers for use herein include alkyl and hydroxyalkylcelluloses (U.S. Pat. No. 4,000,093), polyoxyethylenes,polyoxypropylenes and copolymers thereof, and nonionic and anionicpolymers based on terephthalate esters of ethylene glycol, propyleneglycol and mixtures thereof.

Heavy metal sequestrants and crystal growth inhibitors are also suitablefor use in the detergent, for example diethylenetriamine penta(methylenephosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate,hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate,ethylenediaminotetracetate, ethylenediamine-N,N′-disuccinate in theirsalt and free acid forms.

Suitable for use in the detergent composition described herein is also acorrosion inhibitor, for example organic silver coating agents(especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen,Germany), nitrogen-containing corrosion inhibitor compounds (for examplebenzotriazole and benzimadazole—see GB-A-1137741) and Mn(II) compounds,particularly Mn(II) salts of organic ligands.

Other suitable components for use in the detergent composition hereininclude enzyme stabilizers, for example calcium ion, boric acid andpropylene glycol.

Other suitable components for use in the detergent composition hereininclude humectants, for example, as described in U.S. Patent ApplicationPublication No. 2015/0329807.

Suitable rinse additives are known in the art. Commercial rinse aids fordishwashing typically are mixtures of low-foaming fatty alcoholpolyethylene/polypropylene glycol ethers, solubilizers (for examplecumene sulfonate), organic acids (for example citric acid) and solvents(for example ethanol). The function of such rinse aids is to influencethe interfacial tension of the water in such a way that it is able todrain from the rinsed surfaces in the form of a thin coherent film, sothat no water droplets, streaks, or films are left after the subsequentdrying process. European Patent 0 197 434 B1 describes rinse aids whichcontain mixed ethers as surfactants. Rinse additives such as fabricsofteners and the like are also contemplated and suitable forencapsulation in a film according to the disclosure herein.

Suitable liquid laundry detergents (LLD) for testing the compatibilityof the water-soluble films described herein with liquid laundrydetergents are described in the tables below:

LLD One Wt % Monoethanolamine 8-9% Dodecylbenzenesulfonic Acid 22-26%Oleic Acid 18-21% Lauryl Alcohol Ethoxylate 22-26% Propylene Glycol 8-11% Diethylene Glycol  8-11% Water 4-7%

LLD Two Wt % Monoethanolamine 8-9% Dodecylbenzenesulfonic Acid 22-26%Oleic Acid 18-21% Lauryl Alcohol Ethoxylate 22-26% Propylene Glycol 5-7%Diethylene Glycol 5-7% Glycerin 5-7  Water 4-8%

Methods of Use

The films and articles described herein, as well as compositionscontained therein, may be used to treat a substrate, e.g., fabric or ahard surface, for example by contacting the substrate with the film,article, and/or composition contained therein. The contacting step mayoccur manually or in an automatic machine, e.g., an automatic (top orfront-loading) laundry machine or an automatic dishwashing machine. Thecontacting step may occur in the presence of water, which may be at atemperature up to about 80° C., or up to about 60° C., or up to about40° C., or up to about 30° C., or up to about 20° C., or up to about 15°C., or up to about 10° C., or up to about 5° C. As noted above, thepresent films and articles made therefrom are particularly suited forcold water dissolution and therefore provide benefits in cold-waterwashes (e.g., from about 1° C. to about 30° C., or from about 5° C. toabout 20° C.). The contacting step may be followed by a multi-rinsecycle or even by a single rinse cycle; because the film has gooddissolution properties, less water is required to dissolve the filmand/or release the contents contained therein.

Dissolution Chamber Residue Test

A water-soluble film characterized by or to be tested for undissolvedresidue according to the Dissolution Chamber (DC) Test is analyzed asfollows using the following materials:

1. Beaker (4000 ml);

2. Stainless steel washers (3.5″ (88.9 mm) OD, 1.875″ ID (47.6 mm),0.125″ (3.18 mm) thick);

3. Styrene-butadiene rubber gaskets (3.375″ (85.7 mm) OD, 1.91″ ID (48.5mm), 0.125″ thick (3.18 mm));

4. Stainless steel screens (3.0″ (76.2 mm) OD, 200×200 mesh, 0.0021″(0.053 mm) wire OD, 304SS stainless steel wire cloth);

5. Thermometer (0° C. to 100° C., accurate to +/−1° C.);

6. Cutting punch (1.5″ (38.1 mm) diameter);

7. Timer (accurate to the nearest second);

8. Reverse osmosis (RO) water;

9. Binder clips (size #5 or equivalent);

10. Aluminum pans (2.0″ (50.8 mm) OD); and

11. Sonicator.

For each film to be tested, three test specimens are cut from a selectedtest film having a thickness of 76 μm using the cutting punch. If cutfrom a film web made by a continuous process, the specimens should becut from areas of web evenly spaced along the transverse direction ofthe web (i.e., perpendicular to the machine direction). Each testspecimen is then analyzed using the following procedure:

1. Weigh the film specimen and track the specimen through the test.Record the initial film weight (F_(o)).

2. Weigh a set of two sonicated, clean, and dry screens for eachspecimen and track them through the test. Record the initial screenweights (collectively S_(o) for the two screens combined).

3. Assemble a specimen dissolution chamber by flatly sandwiching thefilm specimen between the center of the two screens, followed by the tworubber gaskets (one gasket on each side between the screen and washer),and then the two washers.

4. Secure the dissolution chamber assembly with four binder clips evenlyspaced around the washers and the clips folded back away from thescreens.

5. Fill the beaker with 1,500 ml of RO water at laboratory roomtemperature (72+/−3° F., 22+/−2° C.) and record the room temperature.

6. Set the timer to a prescribed immersion time of 5 minutes.

7. Place the dissolution chamber assembly into the beaker andimmediately start the timer, inserting the dissolution chamber assemblyat an approximate 45 degree entry angle into the water surface. Thisentry angle helps remove air bubbles from the chamber. The dissolutionchamber assembly rests on the beaker bottom such that the test specimenfilm is positioned horizontally about 10 mm from the bottom. The fourfolded-back binder clips of the dissolution chamber assembly aresuitable to maintain the about 10 mm film clearance from the beakerbottom, however, any other equivalent support means may be used.

8. At the prescribed elapsed prescribed immersion time of 5 minutes,slowly remove the dissolution chamber assembly from the beaker at anapproximate 45 degree angle.

9. Hold the dissolution chamber assembly horizontally over the aluminumpan to catch any drips from the screens and carefully remove the binderclips, washers, and gaskets. Do not break open the sandwiched screens.

10. Place the sandwiched screens (i.e., screen/residual undissolvedfilm/screen) over the aluminum pan and into an oven at 100° C. for 30minutes to dry.

11. Weigh the dried set of sandwiched screens including any residualundissolved film therein. Measure and add to this dried screen weightany dried film drippings captured in and recovered from (e.g., byscraping) the pan when the dissolution chamber assembly was firstremoved from the beaker and during drying. Record the final sandwichedscreen weight (collectively S_(f), including the dried film drippings).

12. Calculate % residue (“DC residue”) left for the film specimen: % DCresidue=100*((S_(f)−S_(o))/F_(o)).

13. Clean the sandwiched screens by soaking them in a beaker of RO waterfor about 20 minutes. Then, take them apart and do a final rinse in thesonicator (turned on and filled with RO water) for at least 5 minutes oruntil no residue is visible on the screens.

Suitable behavior of water-soluble films according to the disclosure ismarked by DC residue values of about 35 wt. % or less, about 40 wt. % orless, about 45 wt. % or less or about 48 wt. % or less as measured bythe DC Test. Generally, lower DC residue values are desirable to reducethe likelihood of residual film remaining on a washed article afteraggressive washing conditions (e.g., in low water conditions (such as inoverloading of the washing machine) and in cold wash water conditions).In various embodiments, the water-soluble film has a DC residue value ofat least 1, 2, 5, 10, 12, 15, 25, 30, or 35 wt. % and/or up to about 15,20, 30, 35, 40, 45, or 48 wt. %; (e.g., about 3 wt. % to about 48 wt. %,about 5 wt. % to about 48 wt. %, or about 12 wt. % to about 48 wt. %, orabout 25 wt. % to about 48 wt. %, or about 10 wt. % to about 45 wt. %,or about 20 wt. % to about 45 wt. %, about 25 wt. % to about 40 wt. %,about 30 wt. % to 40 wt. %, about 3 wt. % to about 40 wt. %, or about 3wt. % to about 35 wt. %.).

Dissolution and Disintegration Test (MSTM 205)

A film can be characterized by or tested for Dissolution Time andDisintegration Time according to the MonoSol Test Method 205 (MSTM 205),a method known in the art. See, for example, U.S. Pat. No. 7,022,656.

Apparatus and Materials: 600 mL Beaker

Magnetic Stirrer (Labline Model No. 1250 or equivalent)

Magnetic Stirring Rod (5 cm) Thermometer (0 to 100° C.±1° C.)

Template, Stainless Steel (3.8 cm×3.2 cm)Timer (0-300 seconds, accurate to the nearest second)Polaroid 35 mm slide Mount (or equivalent)MonoSol 35 mm Slide Mount Holder (or equivalent)Distilled water

For each film to be tested, three test specimens are cut from a filmsample that is a 3.8 cm×3.2 cm specimen. If cut from a film web,specimens should be cut from areas of web evenly spaced along thetraverse direction of the web. Each test specimen is then analyzed usingthe following procedure.

Lock each specimen in a separate 35 mm slide mount.

Fill beaker with 500 mL of distilled water. Measure water temperaturewith thermometer and, if necessary, heat or cool water to maintaintemperature at 20° C. (about 68° F.).

Mark height of column of water. Place magnetic stirrer on base ofholder. Place beaker on magnetic stirrer, add magnetic stirring rod tobeaker, turn on stirrer, and adjust stir speed until a vortex developswhich is approximately one-fifth the height of the water column. Markdepth of vortex.

Secure the 35 mm slide mount in the alligator clamp of the 35 mm slidemount holder such that the long end of the slide mount is parallel tothe water surface. The depth adjuster of the holder should be set sothat when dropped, the end of the clamp will be 0.6 cm below the surfaceof the water. One of the short sides of the slide mount should be nextto the side of the beaker with the other positioned directly over thecenter of the stirring rod such that the film surface is perpendicularto the flow of the water.

In one motion, drop the secured slide and clamp into the water and startthe timer. Disintegration occurs when the film breaks apart. When allvisible film is released from the slide mount, raise the slide out ofthe water while continuing to monitor the solution for undissolved filmfragments. Dissolution occurs when all film fragments are no longervisible and the solution becomes clear.

The results should include the following: complete sampleidentification; individual and average disintegration and dissolutiontimes; and water temperature at which the samples were tested.

Film disintegration times (I) and film dissolution times (I) can becorrected to a standard or reference film thickness using theexponential algorithms shown below in Equation 1 and Equation 2,respectively.

I _(corrected) =I _(measured)×(reference thickness/measuredthickness)^(1.93)  [1]

S _(corrected) =S _(measured)×(reference thickness/measuredthickness)^(1.83)  [2]

Tensile Strength Test and Modulus Test

A water-soluble film characterized by or to be tested for tensilestrength according to the Tensile Strength (TS) Test and modulus (ortensile stress) according to the Modulus (MOD) Test is analyzed asfollows. The procedure includes the determination of tensile strengthand the determination of modulus at 10% elongation according to ASTM D882 (“Standard Test Method for Tensile Properties of Thin PlasticSheeting”) or equivalent. An INSTRON tensile testing apparatus (Model5544 Tensile Tester or equivalent) is used for the collection of filmdata. A minimum of three test specimens, each cut with reliable cuttingtools to ensure dimensional stability and reproducibility, are tested inthe machine direction (MD) (where applicable) for each measurement.Tests are conducted in the standard laboratory atmosphere of 23±2.0° C.and 35±5% relative humidity. For tensile strength or modulusdetermination, 1″-wide (2.54 cm) samples of a single film sheet having athickness of 76 μm are prepared. The sample is then transferred to theINSTRON tensile testing machine to proceed with testing while minimizingexposure in the 35% relative humidity environment. The tensile testingmachine is prepared according to manufacturer instructions, equippedwith a 500 N load cell, and calibrated. The correct grips and faces arefitted (INSTRON grips having model number 2702-032 faces, which arerubber coated and 25 mm wide, or equivalent). The samples are mountedinto the tensile testing machine and analyzed to determine the 100%modulus (i.e., stress required to achieve 100% film elongation) andtensile strength (i.e., stress required to break film).

Generally, higher TS values are desirable because they correspond tostronger pouch seals when the film is the limiting or weakest element ofa seal

Generally, higher MOD values are desirable because they correspond topouches having a greater stiffness and a lower likelihood of deformingand sticking to each other when loaded on top of each other duringproduction or in final consumer packaging. Further, MOD values at 100%elongation correspond to the ability of the film to maintain stiffnessand pouch tautness when in contact with liquid pouch contents.

Without intending to be bound by theory, it is believed that the changein modulus over time can be used to predict if a pouch containing aliquid laundry detergent will remain taut over time or if the pouch willlose tautness and take on a loose and droopy appearance and feel. Inparticular, without intending to be bound by theory, it is believed thata film having a greater positive change in modulus (A modulus) (positiveslope or increase in modulus) over time will remain more taut for up toat least 12 weeks under ambient conditions or up to 38° C. and 80% RHconditions compared to films having a A modulus of about 0 and willremain substantially more taut than films having a negative A modulus.

Liquid Release Test

A water-soluble film and/or pouch characterized by or to be tested fordelayed solubility according to the Liquid Release Test is analyzed asfollows using the following materials:

-   -   2 L beaker and 1.2 liters of deionized (DI) water    -   Water soluble pouch to be tested; the film has a thickness of 88        μm; the pouch is pre-conditioned for two weeks at 38° C.    -   Thermometer    -   Wire cage    -   Timer

Before running the experiment, ensure that enough DI water is availableto repeat the experiment five times, and ensure that the wire cage andbeaker are clean and dry.

The wire frame cage is a plastic coated wire cage (4″×3.5″×2.5″, orabout 10 cm×9 cm×6 cm) with no sharp edges, or equivalent. The gauge ofthe wire should be about 1.25 mm and the wire should have openings thesize of 0.5 inch (1.27 cm) squares. An example image of a cage 28 withtest pouches 30 is shown in FIG. 1.

To set up for the test, carefully place the water soluble pouch in thecage while not scratching the pouch on the cage and allowing free spacefor the pouch to move. Do not bind the pouch tightly with the wire cage,while still ensuring it is secure and will not come out of the cage. Theorientation of the pouch in the cage should be such that the naturalbuoyancy of the pouch, if any, is allowed (i.e. the side of the pouchthat will float to the top should be placed towards the top). If thepouch is symmetrical, the orientation of the pouch generally would notmatter.

Next, fill the 2 L beaker with 1200 milliliters of 20° C. DI water.

Next, lower the wire frame cage with the enclosed pouch into the water.Ensure that the cage is 1 inch (2.54 cm) from the bottom of the beaker.Be sure to fully submerge the pouch on all sides. Ensure that the cageis stable and will not move and start a timer as soon as the pouch islowered into the water. The position of the cage with respect to thewater in the beaker can be adjusted and maintained by any suitablemeans, for example by using a clamp fixed above the beaker, and a rodattached to the top of the cage. The clamp can engage the rod to fix theposition of the cage, and tension on the clamp can be lowered in orderto lower the cage into the water. Other means of frictional engagementcan be used in the alternative to a clamp, for example a collar with aset screw, as shown in FIG. 2 (set screw not shown). FIG. 2 shows abeaker 30 resting on a stand 40, the stand holding a rod 50 for loweringa cage 10 (not shown) into the beaker 30, the rod 50 being able to holda fixed vertical position by use of a collar 60 having a set screw (notshown) that engages the rod 50, for example by friction or by engagementwith a hole (not shown) in the rod 50.

Liquid content release is defined as the first visual evidence of theliquid leaving the submerged pouch.

Use the timer to record when the liquid content is released in to thesurrounding water (Release Time) with a stopping point of 45 seconds.

A pass or fail grade will be given to each pouch. A pass grade isreceived if the soluble pouch retained its liquid for 30 seconds orlonger. A fail grade is received if the soluble pouch did not retain itsliquid for at least 30 seconds.

Repeat this process with new DI water and a new water soluble pouch fivetimes for each film being tested.

A total of at least 15 pouches are tested for each film sample typeunless reported otherwise.

Compression Test Measurement

A water-soluble film and/or pouch characterized by or to be tested forthe ability of a water soluble capsule to resist a mechanicalcompression strength of a minimum of 300 N according to the CompressionTest Measurement is analyzed as follows using the following materials:

-   -   Instron Model 5544 (or equivalent)    -   At least 15 water-soluble pouch or capsule to be tested the film        has a thickness of 88 μm; the pouch is pre-conditioned for at        least 24 hours at 23±1° C. ad 50±4% Relative Humidity.    -   Zipper type bags    -   Two flat plates (Top plate: 10 KN Max load T1223-1022/Bottom        plate: 100 KN Max load T489-74)    -   Load cell (Static load ±2 kN, Max spindle torque 20 Nm, bolt        torque 25 Nm, and weight 1.2 kg)    -   Marker    -   Allen wrench (6 mm)

The pouch is inspected for leaks and then placed into a zippered bag(approximately 57 micron thick on each side). Seal the bag with minimalair inside. Label the bag with the sample name and number.

Open the method for compression test. Ramp speed should be 4 mm/s.

Carefully place the sample, cavity side down, between the two platesmaking sure the pouch is on the center of the bottom plate. Move capsuleinside the bag away from any edges.

Press start to run the test. As the two plates come together, the pouchwill burst. Record the compression strength and the location on thepouch where the rupture occurred. Repeat this process for all samples.

Suitable behavior of water-soluble films according to the disclosure ismarked by compression values of at least about 300 N and less than about2000N as measured by the Compression Test Measurement.

Film Swelling Test Measurement

A water-soluble film and/or pouch characterized by or to be tested forthe resistance to swelling in the presence of a liquid composition isanalyzed as follows.

Three samples of a film are taken from different locations of the filmfrom a roll on a larger film sample. Three 2 inch by 2 inch squares(about 5 cm×5 cm) are cut with a punch. The weight and gauge of eachsample is measured and recorded.

For each sample, the weight of a petri dish is tared out and 12 g of atesting fluid is added to the dish. A film sample is added to the petridish in the center of the base. Additional testing fluid is added until20 g of testing fluid is present in the petri dish and the film sampleis completely covered and submerged in the testing fluid. A cap or coveris placed onto the petri dish.

Each petri dish is wrapped with parafilm and placed in a conditioningoven at a temperature of 38° C. and an RH of 80%, for 24 hours.

A measuring grid is placed on a horizontal surface. After conditioning,the petri dishes are unwrapped and the film samples removed. The filmsamples are placed on the measuring grid. The film sample length andwidth are recorded, noting which is the machine direction. The testingfluid is wiped from the surface of the film sample, using a KimWipe® orequivalent. The weight and gauge of the film sample is recorded.

The swelling ratio is the ratio of the weight added to the film over theinitial weight (e.g., (weight final−weight initial)/weight initial)).

For the water-soluble films of the disclosure including a blend of PVOHresins, suitable behavior of water-soluble films according to thedisclosure is characterized relative to a comparative film which isidentical but for the second PVOH copolymer being the sole resin and theamount of that second PVOH copolymer in the comparative film being equalto the total amount of resins in the inventive water-soluble film. Inparticular, suitable behavior of water-soluble films according to thedisclosure are marked by a swelling ratio value that is no greater than60% of the swelling ratio value of a comparative film which is identicalbut for the second PVOH copolymer being the sole resin and the amount ofthat second PVOH copolymer in the comparative film being equal to thetotal amount of resins in the inventive water-soluble film, as measuredby the Film Swelling Test Measurement.

Swelling introduces a change in the dimensions of the film which canresult in a less taut package, as the final film area is greater, butencapsulating the same volume of liquid.

Crystallinity Test Measurement

A water-soluble film and/or pouch characterized by or to be tested forthe crystallinity of the film is analyzed as follows.

Film samples are conditioned in an environment of 22° C. and 40% RH forat least 24 hours. A 3 mm by 3 mm moisture-conditioned film sample isthen mounted in a sealed cell. A WAXD measurement is then performed witha D8 Discover x-ray diffractometer or equivalent, equipped with atwo-dimensional detector (Bruker AXS Co., Ltd.) using an exposure timeof 600 seconds.

A one dimensional profile (Intensity vs. 2theta) is obtained byaveraging ring like diffraction data of a photographic image. A blankprofile is obtained and subtracted from the sample profile to provide abackground subtracted profile. A straight line connecting the intensityvalues of diffraction angles at 15 degrees and 25 degrees is subtractedform the background subtracted profile to provide a baseline.

Let a Gaussian function reproduce intensity values in the range ofdiffraction angles from 15 degrees to 17.6 degrees and intensity valuesin the range from 21 degrees to 21.6 degrees as a scattering functionfrom amorphous PVOH. Find a peak position, a peak width, and a peakheight of the Gaussian function with least squares fitting. Reproducediffraction signals of 19.5 degrees and 23 degrees which are attributedto the 110 diffraction and the 200 diffraction from the PVOH crystalwith two Gaussian functions. Find a peak position, a peak width, and apeak height with least squares fitting. The parameters of the Gaussianfunction assumed to be amorphous PVOH are fixed. The fitting parametersof the Gaussian functions regarded as the crystals are fixed, and threeparameters of the Gaussian function attributed to amorphous PVA areagain least squares fitted. Find the integrated intensity values of thethree Gaussian functions. The apparent crystallinity is calculated as apercentage of the sum of the integrated intensity values of the twoGaussian functions attributed to crystal PVOH in the total integratedintensity values.

Without intending to be bound by theory, it is believed that thecrystallinity of a water-soluble film can be reduced by increasing thelevel on anionic monomer unit included in the resin, decreasing thedegree of hydrolysis of the resin, increasing the amount of plasticizerprovided in the film formulation, and/or cooling the water-soluble filmquickly after casting. Further, without intending to be bound by theory,it is believed that, in general, the lower the crystallinity of a film,the more the film will swell when in contact with a liquid composition.

The water soluble films in accordance with the disclosure can be betterunderstood in light of the following examples, which are merely intendedto illustrate the water soluble films and are not meant to limit thescope thereof in any way.

EXAMPLES Example 1: Single Resin Film

Example 1 represents a water-soluble film which was formed with a singlePVOH copolymer, Resin A. Resin A was a fully hydrolyzed (99% degree ofhydrolysis) PVOH polymer including 5 mol. % level of incorporation ofmethyl acrylate comonomer that had 70% of the rings opened, having alevel of pendant groups of 5 mol. %, and having a 4% solution viscosityat 20° C. of 20 cP. The film included (i) Resin A (100 weight parts),(ii) glycerin plasticizer (24.67 weight parts per hundred parts resin(phr)), (iii) sorbitol plasticizer (13.12 phr), (iv) trimethylolpropaneplasticizer (5.33 phr), (v) propylene glycol plasticizer (0.50 phr) (vi)filler (4.85 phr of bulking agent and anti-blocking agent, combined),(vii) surfactants and other process aids (3.15 phr includingantioxidant, defoamer, amine oxide surfactant, and cationic surfactant),and residual water (about 5-12 phr). Aqueous compositions of theforegoing were cast and dried to form 76 μm thick film samples, whichwere tested for DC residue values by the above method. The resin andfilm properties for samples of films according to Example 1 at ambientconditions (i.e., 23° C. and 35% relative humidity (RH)), prior toexposure to a liquid laundry detergent, are summarized in Table 1. InTable 1, the pendant group (P) content for the film is provided on amolar basis relative to the PVOH resins in the film (i.e., excluding theplasticizers and the other non-resin components thereof), and the Pvalue further indicates that the pendant group corresponds to a methylacrylate comonomer unit (A).

Example 2: Single Resin Film

Example 2 represents water-soluble films which were formed including asingle PVOH copolymer, Resin B. Resin B was a commercially availablePVOH copolymer having a specification degree of hydrolysis of 88-92%,having 4.0 mol. % level of incorporation of maleic anhydride (sodiumsalt) comonomer and 8.0 mol. % pendant groups, and having a specified 4%solution viscosity at 20° C. of 15-20 cP. The film included (i) Resin B(100 weight parts), (ii) glycerin plasticizer (23.9 weight parts perhundred parts resin (phr)), (iii) sorbitol plasticizer (17.46 phr), (iv)trimethylolpropane plasticizer (4.05 phr), (v) propylene glycolplasticizer (0.47 phr), (vi) filler (1.78 phr antiblocking agent),(viii) surfactants and other process aids (3.06 phr includingantioxidant, defoaming agent, amine oxide surfactant, and cationicsurfactant), and residual water (about 5-12 phr). Films were preparedand tested as described in Example 1. Table 1 summarizes the resin andfilm properties for samples of films according to Example 2 at ambientconditions (i.e., 23° C., 35% RH), prior to exposure to a liquid laundrydetergent. In Table 1, the anionic pendant group (P) content for thefilm is provided on a molar basis relative to the PVOH resins in thefilm (i.e., excluding the plasticizers and the other non-resincomponents thereof), and the P value further indicates that the anionicmonomer corresponds to a maleic anhydride comonomer unit (M).

TABLE 1 Resin and Film Data for Examples 1 and 2 Resin Film P P ExampleType μ (cP) DH (%) (mol. %) DC (%) (mol. %) 1 A 20 99 5.00 (A) 9.01 5.00(A) 2 B 17.5 90 8.00 (M) 1.94 8.00 (M)

Thus, Table 1 shows that water-soluble films prepared from a PVOH—alkylacrylate copolymer (Resin A) have higher residue values (DC values)compared to water-soluble film prepared from a PVOH—maleate copolymer(Resin B).

Example 3: Single Resin Film

Example 3 represents a water-soluble film which was formed with Resin Aand non-resin components in the amounts and types as described inExample 1. Films were prepared and tested as described in Example 1. Theresin and film properties for samples of films according to Example 3 atambient conditions (i.e., 23° C., 35% RH), prior to exposure to a liquidlaundry detergent, are summarized in Table 2. In Table 2, the pendantgroup (P) content for the film is provided on a molar basis relative tothe PVOH resins in the film (i.e., excluding the plasticizers and theother non-resin components thereof), and the P value further indicatesthat the pendant group corresponds to a methyl acrylate copolymer unit(A).

Example 4: Single Resin Film

Example 4 represents water-soluble films which included a single PVOHcopolymer, Resin B, and non-resin components in the amounts and types asdescribed above in Example 2. Films were prepared and tested asdescribed in Example 1. Table 2 summarizes the resin and film propertiesfor samples of films according to Example 4 at ambient conditions (i.e.,23° C., 35% RH), prior to exposure to a liquid laundry detergent. InTable 2, the anionic pendant group (P) content for the film is providedon a molar basis relative to the PVOH resins in the film (i.e.,excluding the plasticizers and the other non-resin components thereof),and the P value further indicates that the anionic monomer correspondsto a maleic anhydride comonomer unit (M).

TABLE 2 Resin and Film Data for Examples 3 and 4 Resin Film P P ExampleType μ (cP) DH (%) (mol. %) DC (%) (mol. %) 3 A 20 99 5.00 (A) 21.2 5.00(A) 4 B 17.5 90 8.00 (M) 0.86 8.00 (M)

Thus, Table 2 shows that water-soluble films prepared from a PVOH—alkylacrylate copolymer (Resin A) have higher residue values (DC values)compared to water-soluble film prepared from a PVOH—maleate copolymer(Resin B). Further, a comparison of Examples 1 and 2 to Examples 3 and 4demonstrates that the films prepared from the PVOH-alkyl acrylatecopolymer (Resin A) had higher residue values relative to the filmsprepared from the PVOH-maleate copolymer (Resin B), at both highplasticizer levels (e.g., greater than 30 phr total, 1 and 2) and a lowplasticizer levels (e.g., less than 30 phr total, 3 and 4).

Examples 5-8: Two-Resin Blend Films

Examples 5-8 represent water-soluble films which were formed, each filmincluded a blend of the two copolymers, Resin A and Resin B. Specificblends include 80 wt. % Resin A and 20 wt. % Resin B (Example 5), 60 wt.% Resin A and 40 wt. % Resin B (Example 6), 40 wt. % Resin A and 60 wt.% Resin B (Example 7), and 20 wt. % Resin A and 80 wt. % Resin B(Example 8). The blend films included two resins that made up 100% ofthe resin in the film, while plasticizers and other non-resin componentswere present in the amounts and types as described for Example 1. Filmswere prepared and tested as described in Example 1. Table 3 summarizesthe resin and film properties for Examples 5-8. The first and lastentries for Table 3 represent the single-resin limit for the filmformulation (i.e., Examples 1 and 2), while the remaining valuesrepresent the two-resin blend formulations. In Table 3, the pendantgroup (P) content for the film is provided on a molar basis relative toall of the polymeric resin in the film (i.e., including both resinspresent but excluding the plasticizers and the other non-resincomponents thereof), and the P values further indicate whether theycorrespond to a methyl acrylate comonomer unit (A) or a maleic anhydridecomonomer unit (M).

TABLE 3 Resin and Film Data for Examples 5-8 Resins Film Exam- Amt. Amt.% Crystal- P (mol. ple Type (wt. %) Type (wt. %) DC (%) linity %) 1 A100 B 0 9.01* 18.9* 5.00 (A) 5 A 80 B 20 9.67* 18.7* 5.6 (A/M) 6 A 60 B40 17.62* 20.1* 6.2 (A/M) 7 A 40 B 60 12.32* 18.4* 6.8 (A/M) 8 A 20 B 803.06* 15.2* 7.4 (A/M) 2 A 0 B 100 1.94* 13.8 8.00 (M)

Examples 5-8 illustrate that water-soluble films including PVOH resinblends having a first copolymer comprising a first anionic monomer unitand a second copolymer having a second anionic monomer unit, asdescribed herein, can exhibit a combination of substantiallyadvantageous, yet competing, physical and chemical properties when thePVOH resin blends are selected in view of their particular blendconstituents, the relative amounts of the blend constituents, or both.For example, as noted above, films that are particularly suitable forcomposition-in-pouch delivery applications satisfy at least one of (a) aDC residue value of about 35 wt. % or less to reduce or eliminate filmresidue on articles in washing applications, or (b) a crystallinity ofat least 15% to create stiff pouches less likely to soften and droopwhen formed into pouches enclosing liquid compositions. Desirably, afilm meets criteria (a) and (d).

As illustrated in the single-resin film data of Examples 1 and 2,however, desirable DC values are often in competition with crystallinityvalues. For example, the film of Example 2 (Resin B) had a desirably lowDC residue value but a poor crystallinity value.

As shown in Examples 5-8, it unexpectedly has been found that certainwater-soluble films containing PVOH resin blends with at a first PVOHcopolymer comprising a first anionic monomer as described herein and asecond PVOH copolymer comprising a second anionic monomer as describedherein meet criteria (a) and (b). In Table 3, film properties markedwith an “*” satisfy criteria (a) or (b). From the data, it is seen thatfilms including PVOH resin blends including two PVOH anionic copolymers,as exemplified by Examples 5-8, generally meet criteria (a) and (b) forA/B blend ratios ranging from about 20/80 to about 80/20 (w/w,respectively).

Examples 9-12: Two-Resin Blend Films

Examples 9-12 represent water-soluble films which were formed, each filmincluded a blend of the two copolymers, Resin A and Resin B. Specificblends include 80 wt. % Resin A and 20 wt. % Resin B (Example 9), 60 wt.% Resin A and 40 wt. % Resin B (Example 10), 40 wt. % Resin A and 60 wt.% Resin B (Example 11), and 20 wt. % Resin A and 80 wt. % Resin B(Example 12). The blend films included two resins that made up 100% ofthe resin in the film, while plasticizers and other non-resin componentswere present in the amounts and types as described for Example 3. Filmswere prepared and tested as described for Example 1. Table 4 summarizesthe resin and film properties for Examples 9-12. The first and lastentries for Table 4 represent the single-resin limit for the filmformulation (i.e., Examples 3 and 4), while the remaining valuesrepresent the two-resin blend formulations. In Table 4, the pendantgroup (P) content for the film is provided on a molar basis relative toall of the polymeric resin in the film (i.e., including both resinspresent but excluding the plasticizers and the other non-resincomponents thereof), and the P values further indicate whether theycorrespond to a methyl acrylate comonomer unit (A) or a maleic anhydridecomonomer unit (M).

TABLE 4 Resin and Film Data for Examples 9-12 Resins Film Amt. % Exam-(wt. Amt. Crystallinity P (mol. ple Type %) Type (wt. %) DC (%) (≥15%)%) 3 A 100 B 0 21.20* Not 5.0 (A) Determined 9 A 80 B 20 18.63* Not 5.6Determined (A/M) 10 A 60 B 40 19.35* Not 6.2 Determined (A/M) 11 A 40 B60 16.16* 18.1* 6.8 (A/M) 12 A 20 B 80 14.3* 19.3* 7.4 (A/M) 4 A 0 B 1000.86* 14.7 8.00 (M)

Examples 9-12 illustrate that water-soluble films including PVOH resinblends having a first copolymer comprising a first anionic monomer unitand a second copolymer having a second anionic monomer unit, asdescribed herein, can exhibit a combination of substantiallyadvantageous, yet competing, physical and chemical properties when thePVOH resin blends are selected in view of their particular blendconstituents, the relative amounts of the blend constituents, or both.

As illustrated in the single-resin film data of Examples 3 and 4,however, desirable DC values are often in competition with crystallinityvalues. For example, the film of Example 4 (Resin B) had a desirably lowDC residue value but a poor crystallinity value.

As shown in Examples 9-12, it unexpectedly has been found that certainwater-soluble films containing PVOH resin blends with at a first PVOHcopolymer comprising a first anionic monomer as described herein and asecond PVOH copolymer comprising a second anionic monomer as describedherein meet one or both of criteria (a) and (b). In Table 4, filmproperties marked with an “*” satisfy criteria (a) or (b). From thedata, it is seen that films including PVOH resin blends including twoPVOH anionic copolymers, as exemplified by Examples 9-12, generally meetcriteria (a) and (b) for A/B blend ratios ranging from about 20/80 toabout 80/20 (w/w, respectively).

Examples 13-18: Single Resin Film Exposed to LLD

Films prepared with Resin A and non-resin components in the types andamounts described in Example 1 were exposed to liquid laundry detergentone (LLD 1) as described herein. The films were prepared as described inExample 1 and were tested for DC residue values by the above methodafter storing in contact with the LLD 1 for 3, 6, or 12 weeks at ambientconditions (23° C., 35% RH) or a high stress, 38° C., 80% RHenvironment. The average DC values are summarized in Table 5. In Table5, the pendant group (P) content for the film is provided on a molarbasis relative to the PVOH resins in the film (i.e., excluding theplasticizers and the other non-resin components thereof), and the Pvalue further indicates that the pendant group corresponds to a methylacrylate comonomer unit (A). The first entry for Table 5 represent thesingle-resin limit for the film formulation (e.g., as similarlyrepresented in Examples 1).

TABLE 5 Resin and Film Data for Examples 13-18 Weeks Environment ExampleType Stored Conditions DC (%) P (mol. %) 1 A 0 23° C., 35% RH 9.01* 5.0(A) 13 A 3 23° C., 35% RH 33.36* 5.0 (A) 14 A 6 23° C., 35% RH 32.13*5.0 (A) 15 A 12 23° C., 35% RH 48.45 5.0 (A) 16 A 3 38° C., 80% RH 46.975.0 (A) 17 A 6 38° C., 80% RH 42.95 5.0 (A) 18 A 12 38° C., 80% RH 43.175.0 (A)

Thus, Table 5 demonstrates that for a single resin film having a PVOHcopolymer including an acrylate modification and pendant groups, the DCresidue values increase upon storage at ambient temperature andhumidity, and increase even further when stored at 38° C. and 80% RH.Further, by comparing the DC residue values of Example 1 with the DCresidue values of Examples 13-18, it can be seen that for a single resinfilm having a PVOH copolymer including an acrylate modification andpendant groups, the film residue generally increases after exposure toliquid laundry detergent and storage. In Table 5, film properties markedwith an “*” satisfy criteria (a), as described in Examples 5 to 12.

Examples 19-24: Single Resin Film Exposed to LLD

Films prepared with Resin A and non-resin components in the types andamounts described in Example 3 were exposed to liquid laundry detergentone (LLD 1) as described herein. The films were prepared as described inExample 1 and tested as described in Examples 13 to 18. The average DCvalues are summarized in Table 6. In Table 6, the pendant group (P)content for the film is provided on a molar basis relative to the PVOHresins in the film (i.e., excluding the plasticizers and the othernon-resin components thereof), and the P value further indicates thatthe pendant group corresponds to a methyl acrylate comonomer unit (A).The first entry for Table 6 represent the single-resin limit for thefilm formulation (i.e., Example 3).

TABLE 6 Resin and Film Data for Examples 19-24 Weeks Environment ExampleType Stored Conditions DC (%) P (mol. %) 3 A 0 23° C., 35% RH 21.20* 5(A) 19 A 3 23° C., 35% RH 32.61* 5 (A) 20 A 6 23° C., 35% RH 28.21* 5(A) 21 A 12 23° C., 35% RH 36.57 5 (A) 22 A 3 38° C., 80% RH 29.91* 5(A) 23 A 6 38° C., 80% RH 41.45 5 (A) 24 A 12 38° C., 80% RH 40.09 5 (A)

Thus, Table 6 demonstrates that for a single resin film having a PVOHcopolymer including an acrylate modification and pendant groups, the DCresidue values increase upon storage at ambient temperature andhumidity, and increase even further when stored at 38° C. and 80% RH.Further, by comparing the DC residue values of Example 3 with the DCresidue values of Examples 19-24, it can be seen that for a single resinfilm having a PVOH copolymer including an acrylate modification andpendant groups, the film residue generally increases after exposure toliquid laundry detergent and storage. In Table 6, film properties markedwith an “*” satisfy criteria (a), as described in Examples 5 to 12.

Further, by comparing the data in Table 5 and Table 6, it can be seenthat the films prepared from the PVOH-alkyl acrylate copolymer (Resin A)having a high plasticizer level (e.g., greater than 30 phr, Examples13-18) demonstrated higher DC residue values relative to the filmsprepared from the PVOH-alkyl acrylate copolymer (Resin A) having a lowplasticizer level (e.g., less than 30 phr total, Examples 19-24).

Examples 25-30: Single Resin Film Exposed to LLD

Films were prepared with Resin B and non-resin components in amounts andtypes as described in Example 2. Films were prepared as described inExample 1 and were exposed to liquid laundry detergent one (LLD 1) asdescribed herein. The films were tested as described in Examples 13 to18. The average DC values are summarized in Table 7. In Table 7, thependant group (P) content for the film is provided on a molar basisrelative to the PVOH resins in the film (i.e., excluding theplasticizers and the other non-resin components thereof), and the Pvalue further indicates that the pendant group corresponds to a maleicanhydride comonomer unit (M).

TABLE 7 Resin and Film Data for Examples 25-30 Weeks Environment ExampleType Stored Conditions DC (%) P (mol. %) 2 B 0 23° C., 35% RH 1.94* 8.00(M) 25 B 3 23° C., 35% RH 8.47* 8.00 (M) 26 B 6 23° C., 35% RH 6.33*8.00 (M) 27 B 12 23° C., 35% RH 13.75* 8.00 (M) 28 B 3 38° C., 80% RH6.19* 8.00 (M) 29 B 6 38° C., 80% RH 5.72* 8.00 (M) 30 B 12 38° C., 80%RH 11.95* 8.00 (M)

Thus, Table 7 demonstrates that for a single resin film having a PVOHcopolymer including a maleate modification and pendant groups, the DCresidue values generally increase upon storage at ambient temperatureand humidity (23° C. and 35% RH), and when stored at 38° C. and 80% RH.Further, by comparing the DC residue values of Example 2 with the DCresidue values of Examples 25-30, it can be seen that for a single resinfilm having a PVOH copolymer including an maleate modification andpendant groups, the film residue generally increases after exposure toliquid laundry detergent and storage, though at a much slower rate thanfor the single resin film having a PVOH copolymer including an acrylatemodification and pendant group (i.e., Examples 13 to 18 in Table 5). InTable 7, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12.

Further, the combined data of Table 5 and Table 7 show thatwater-soluble films that have been exposed to a liquid laundry detergentand stored for 3, 6, or 12 weeks prepared from a PVOH—acrylate copolymer(Resin A) have higher residue values (DC values) compared towater-soluble films that have been exposed to a liquid laundry detergentand stored for 3, 6, or 12 weeks prepared from a PVOH—maleate copolymer(Resin B).

Examples 31-36: Single Resin Film Exposed to LLD

Films were prepared with Resin B and non-resin components in the amountsand types as described in Example 4. Films were prepared as described inExample 1 and were exposed to liquid laundry detergent one (LLD 1) asdescribed herein. The films were tested as described in Examples 13 to18. The average DC values are summarized in Table 8. In Table 8, thependant group (P) content for the film is provided on a molar basisrelative to the PVOH resins in the film (i.e., excluding theplasticizers and the other non-resin components thereof), and the Pvalue further indicates that the pendant group corresponds to a maleicanhydride comonomer unit (M).

TABLE 8 Resin and Film Data for Examples 31-36 Weeks Environment ExampleType Stored Conditions DC (%) P (mol. %) 4 B 0 23° C., 35% RH 0.86* 8.00(M) 31 B 3 23° C., 35% RH 7.94* 8.00 (M) 32 B 6 23° C., 35% RH 4.46*8.00 (M) 33 B 12 23° C., 35% RH 9.10* 8.00 (M) 34 B 3 38° C., 80% RH3.94* 8.00 (M) 35 B 6 38° C., 80% RH 2.69* 8.00 (M) 36 B 12 38° C., 80%RH 6.12* 8.00 (M)

Thus, Table 8 demonstrates that for a single resin film having a PVOHcopolymer including a maleate modification and pendant groups, the DCresidue values remain relatively stable upon storage at ambienttemperature and humidity (23° C. and 35% RH) and when stored at 38° C.and 80% RH. Further, by comparing the DC residue values of Example 4with the DC residue values of Examples 31-36, it can be seen that for asingle resin film having a PVOH copolymer including an maleatemodification and pendant groups, the film residue generally increasesafter exposure to liquid laundry detergent and storage, though at a muchslower rate than for the single resin film having a PVOH copolymerincluding an acrylate modification and pendant group (i.e., Examples 19to 24 in Table 6). In Table 8, film properties marked with an “*”satisfy criteria (a), as described in Examples 5 to 12.

Further, the combined data of Table 6 and Table 8 show thatwater-soluble films that have been exposed to a liquid laundry detergentand stored for 3, 6, or 12 weeks prepared from a PVOH—acrylate copolymer(Resin A) have higher residue values (DC values) compared towater-soluble films that have been exposed to a liquid laundry detergentand stored for 3, 6, or 12 weeks prepared from a PVOH—maleate copolymer(Resin B).

Examples 37-42: Two-Resin Blend Films

Examples 37-42 represent water-soluble films which were formed, eachfilm included a blend of 80 wt. % Resin A and 20 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 1. Films were preparedas described in Example 1. The resulting films were exposed to liquidlaundry detergent one (LLD 1) as described herein and tested asdescribed in Examples 13 to 18. The average DC values are summarized inTable 9. In Table 9, the pendant group (P) content for the film isprovided on a molar basis relative to all of the polymeric resin in thefilm (i.e., including both resins present but excluding the plasticizersand the other non-resin components thereof), and the P values furtherindicate whether they correspond to a methyl acrylate comonomer unit (A)or a maleic anhydride comonomer unit (M).

TABLE 9 Resin and Film Data for Examples 37-42 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 37 80/20 323° C., 35% RH 23.67* 5.6 (A/M) 38 80/20 6 23° C., 35% RH 25.52* 5.6(A/M) 39 80/20 12 23° C., 35% RH 35.53 5.6 (A/M) 40 80/20 3 38° C., 80%RH 34.28* 5.6 (A/M) 41 80/20 6 38° C., 80% RH 33.71* 5.6 (A/M) 42 80/2012 38° C., 80% RH 43.76 5.6 (A/M)

In Table 9, film properties marked with an “*” criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 37-42, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with 80 wt. % of a first PVOH copolymer comprising afirst anionic monomer as described herein and 20 wt. % of a second PVOHcopolymer comprising a second anionic monomer as described hereingenerally meet criteria (a) for A/B blend ratios of about 80/20 (w/w,respectively) up to at least 6 weeks of storage at ambient conditionsand up to at least 6 weeks of storage at 38° C., 80% RH conditions.

Examples 43-48: Two-Resin Blend Films

Examples 43-48 represent water-soluble films which were formed, eachfilm included a blend of 80 wt. % Resin A and 20 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 3. Films were preparedas described in Example 1. The resulting films were exposed to liquidlaundry detergent one (LLD 1) as described herein and tested asdescribed in Examples 13 to 18. The average DC values are summarized inTable 10. In Table 10, the pendant group (P) content for the film isprovided on a molar basis relative to all of the polymeric resin in thefilm (i.e., including both resins present but excluding the plasticizersand the other non-resin components thereof), and the P values furtherindicate whether they correspond to a methyl acrylate comonomer unit (A)or a maleic anhydride comonomer unit (M).

TABLE 10 Resin and Film Data for Examples 43-48 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 43 80/20 323° C., 35% RH 31.02* 5.6 (A/M) 44 80/20 6 23° C., 35% RH 24.53* 5.6(A/M) 45 80/20 12 23° C., 35% RH 27.0* 5.6 (A/M) 46 80/20 3 38° C., 80%RH 35.33* 5.6 (A/M) 47 80/20 6 38° C., 80% RH 35.17* 5.6 (A/M) 48 80/2012 38° C., 80% RH 34.91* 5.6 (A/M)

In Table 10, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 43-48, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with 80 wt. % of a first PVOH copolymer comprising afirst anionic monomer as described herein and 20 wt. % of a second PVOHcopolymer comprising a second anionic monomer as described herein meetcriteria (a) up to at least 12 weeks of storage at ambient conditionsand up to at least 12 weeks of storage at 38° C., 80% RH conditions.

Examples 49-54: Two-Resin Blend Films

Examples 49-53 represent water-soluble films which were formed, eachfilm included a blend of 60 wt. % Resin A and 40 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 1. Films were preparedas described in Example 1 and exposed to liquid laundry detergent one(LLD 1) as described herein. The films were tested as described inExamples 13 to 18. The average DC values values are summarized in Table11. In Table 11, the pendant group (P) content for the film is providedon a molar basis relative to all of the polymeric resin in the film(i.e., including both resins present but excluding the plasticizers andthe other non-resin components thereof), and the P values furtherindicate whether they correspond to a methyl acrylate comonomer unit (A)or a maleic anhydride comonomer unit (M).

TABLE 11 Resin and Film Data for Examples 49-54 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 49 60/40 323° C., 35% RH 20.50* 6.2 (A/M) 50 60/40 6 23° C., 35% RH 23.31* 6.2(A/M) 51 60/40 12 23° C., 35% RH 34.1* 6.2 (A/M) 52 60/40 3 38° C., 80%RH 34.84* 6.2 (A/M) 53 60/40 6 38° C., 80% RH 36.85 6.2 (A/M) 54 60/4012 38° C., 80% RH 23.62* 6.2 (A/M)

In Table 11, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 49-54, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with about 60 wt. % a first PVOH copolymer comprisinga first anionic monomer as described herein and about 40 wt. % of asecond PVOH copolymer comprising a second anionic monomer as describedherein generally meet criteria (a) up to at least 12 weeks of storage atambient conditions and up to at least 12 weeks of storage at 38° C. and80% RH conditions.

Examples 55-60: Two-Resin Blend Films

Examples 55-60 represent water-soluble films which were formed, eachfilm included a blend of 60 wt. % Resin A and 40 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 3. Films were preparedas described in Example 1 and were exposed to liquid laundry detergentone (LLD 1) as described herein. The films were tested as described inExamples 13 to 18. The average DC values are summarized in Table 12. InTable 12, the pendant group (P) content for the film is provided on amolar basis relative to all of the polymeric resin in the film (i.e.,including both resins present but excluding the plasticizers and theother non-resin components thereof), and the P values further indicatewhether they correspond to a methyl acrylate comonomer unit (A) or amaleic anhydride comonomer unit (M).

TABLE 12 Resin and Film Data for Examples 55-60 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 55 60/40 323° C., 35% RH 28.61* 6.2 (A/M) 56 60/40 6 23° C., 35% RH 34.66* 6.2(A/M) 57 60/40 12 23° C., 35% RH 25.83* 6.2 (A/M) 58 60/40 3 38° C., 80%RH 37.30 6.2 (A/M) 59 60/40 6 38° C., 80% RH 31.91* 6.2 (A/M) 60 60/4012 38° C., 80% RH 28.46* 6.2 (A/M)

In Table 12, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 55-60, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with about 60 wt. % of a first PVOH copolymercomprising a first anionic monomer as described herein and about 40 wt.% of a second PVOH copolymer comprising a second anionic monomer asdescribed herein generally meet criteria (a) up to at least 12 weeks ofstorage at ambient conditions and up to at least 12 weeks of storage at38° C. and 80% RH conditions.

Examples 61-66: Two-Resin Blend Films

Examples 61-66 represent water-soluble films which were formed, eachfilm included a blend of 40 wt. % Resin A and 60 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 1. Films were preparedas described in Example 1 and were exposed to liquid laundry detergentone (LLD 1) as described herein. The films were tested as described inExamples 13 to 18. The average DC values are summarized in Table 13. InTable 13, the pendant group (P) content for the film is provided on amolar basis relative to all of the polymeric resin in the film (i.e.,including both resins present but excluding the plasticizers and theother non-resin components thereof), and the P values further indicatewhether they correspond to a methyl acrylate comonomer unit (A) or amaleic anhydride comonomer unit (M).

TABLE 13 Resin and Film Data for Examples 61-66 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 61 40/60 323° C., 35% RH 21.02* 6.8 (A/M) 62 40/60 6 23° C., 35% RH 17.97* 6.8(A/M) 63 40/60 12 23° C., 35% RH 33.31* 6.8 (A/M) 64 40/60 3 38° C., 80%RH 20.14* 6.8 (A/M) 65 40/60 6 38° C., 80% RH 21.38* 6.8 (A/M) 66 40/6012 38° C., 80% RH 32.08* 6.8 (A/M)

In Table 13, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 61-66, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with about 40 wt. % a first PVOH copolymer comprisinga first anionic monomer as described herein and about 60 wt. % of asecond PVOH copolymer comprising a second anionic monomer as describedherein meet criteria (a) up to at least 12 weeks of storage at ambientconditions and up to at least 12 weeks of storage at 38° C., 80% RHconditions.

Examples 67-72: Two-Resin Blend Films

Examples 67-72 represent water-soluble films which were formed, eachfilm included a blend of 40 wt. % Resin A and 60 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other noon-resin components werepresent in the amounts and types as described for Example 3. Films wereprepared according to Example 1 and were exposed to liquid laundrydetergent one (LLD 1) as described herein. The films were tested asdescribed in Examples 13 to 18. The average DC values are summarized inTable 14. In Table 14, the pendant group (P) content for the film isprovided on a molar basis relative to all of the polymeric resin in thefilm (i.e., including both resins present but excluding the plasticizersand the other non-resin components thereof), and the P values furtherindicate whether they correspond to a methyl acrylate comonomer unit (A)or a maleic anhydride comonomer unit (M).

TABLE 14 Resin and Film Data for Examples 67-72 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 67 40/60 323° C., 35% RH 32.05* 6.8 (A/M) 68 40/60 6 23° C., 35% RH 25.38* 6.8(A/M) 69 40/60 12 23° C., 35% RH 29.89* 6.8 (A/M) 70 40/60 3 38° C., 80%RH 28.14* 6.8 (A/M) 71 40/60 6 38° C., 80% RH 31.05* 6.8 (A/M) 72 40/6012 38° C., 80% RH 26.19* 6.8 (A/M)

In Table 14, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 67-72, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with about 40 wt. % a first PVOH copolymer comprisinga first anionic monomer as described herein and about 60 wt. % of asecond PVOH copolymer comprising a second anionic monomer as describedherein meet criteria (a) up to at least 12 weeks of storage at ambientconditions and up to at least 12 weeks of storage at 38° C., 80% RHconditions.

Examples 73-78: Two-Resin Blend Films

Examples 73-78 represent water-soluble films which were formed, eachfilm included a blend of 20 wt. % Resin A and 80 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 1. Films were preparedas described in Example 1 and exposed to liquid laundry detergent one(LLD 1) as described herein. The films were tested as described inExamples 13 to 18. The average DC values are summarized in Table 15. InTable 15, the pendant group (P) content for the film is provided on amolar basis relative to all of the polymeric resin in the film (i.e.,including both resins present but excluding the plasticizers and theother non-resin components thereof), and the P values further indicatewhether they correspond to a methyl acrylate comonomer unit (A) or amaleic anhydride comonomer unit (M).

TABLE 15 Resin and Film Data for Examples 73-78 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 73 20/80 323° C., 35% RH 20.61* 7.4 (A/M) 74 20/80 6 23° C., 35% RH 19.25* 7.4(A/M) 75 20/80 12 23° C., 35% RH 19.37* 7.4 (A/M) 76 20/80 3 38° C., 80%RH 14.41* 7.4 (A/M) 77 20/80 6 38° C., 80% RH 17.59* 7.4 (A/M) 78 20/8012 38° C., 80% RH 6.99* 7.4 (A/M)

In Table 15, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 73-78, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with about 20 wt. % a first PVOH copolymer comprisinga first anionic monomer as described herein and about 80 wt. % of asecond PVOH copolymer comprising a second anionic monomer as describedherein meet criteria (a) up to at least 12 weeks of storage at ambientconditions and up to at least 12 weeks of storage at 38° C., 80% RHconditions.

Examples 79-84: Two-Resin Blend Film

Examples 79-84 represent water-soluble films which were formed, eachfilm included a blend of 20 wt. % Resin A and 80 wt. % Resin B. Theblend films included the two resins that made up 100% of the resin inthe film, while plasticizers and other non-resin components were presentin the amounts and types as described for Example 3. Films were preparedas described in Example 1 and exposed to liquid laundry detergent one(LLD 1) as described herein. The films were as described in Examples 13to 18. The average DC values are summarized in Table 16. In Table 16,the pendant group (P) content for the film is provided on a molar basisrelative to all of the polymeric resin in the film (i.e., including bothresins present but excluding the plasticizers and the other non-resincomponents thereof), and the P values further indicate whether theycorrespond to a methyl acrylate comonomer unit (A) or a maleic anhydridecomonomer unit (M).

TABLE 16 Resin and Film Data for Examples 79-84 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 79 20/80 323° C., 35% RH 7.40* 7.4 (A/M) 80 20/80 6 23° C., 35% RH 39.70 7.4 (A/M)81 20/80 12 23° C., 35% RH 20.49* 7.4 (A/M) 82 20/80 3 38° C., 80% RH17.75* 7.4 (A/M) 83 20/80 6 38° C., 80% RH 14.67* 7.4 (A/M) 84 20/80 1238° C., 80% RH 12.77* 7.4 (A/M)

In Table 16, film properties marked with an “*” satisfy criteria (a), asdescribed in Examples 5 to 12. As shown in Examples 79-84, itunexpectedly has been found that certain water-soluble films containingPVOH resin blends with about 20 wt. % a first PVOH copolymer comprisinga first anionic monomer as described herein and about 80 wt. % of asecond PVOH copolymer comprising a second anionic monomer as describedherein generally meet criteria (a) up to at least 12 weeks of storage at38° C., 80% RH conditions.

Example 85: Film Swelling

Water-soluble films were formed from single resins or blends of the twocopolymer Resins A and B. Films were prepared having weight ratios ofResin A to Resin B of 100/0, 80/20, 60/40, 40/60, 30/70, 20/80, and0/100. Resin A, B, or the combination of Resin A and Resin B made up100% of the resin in the films prepared herein, while plasticizers andother non-film components were present in the amounts and types asdescribed for Example 1. The films were tested for swelling ratio ineach of propylene glycol, polyethylene glycol (PEG) 200, glycerin, anddiglycerol, accordance with the Film Swelling Test described herein. Theaverage swelling ratios are summarized in Table 17.

TABLE 17 Average Swelling Ratios of Films in Various Solvents Ratio ofResin Propylene A/Resin B glycol PEG 200 Glycerin Diglycerol 100/0 0.0793 −0.015 0.7478 0.0599 80/20 0.1825 −0.0605 0.7425 0.1327 60/400.1599 −0.0558 0.6189 0.1451 40/60 0.2067 −0.0153 0.9806 0.1678 30/700.2105 Not Determined 1.1194 Not Determined 20/80 0.4744 0.0179 1.67230.3428  0/100 1.7167 0.3367 10.6665 0.7266

As shown in Table 17, as the amount of PVOH-maleate copolymer (Resin B)increases, the swelling value of the water-soluble film generallyincreases, and a significant increase is observed for films including noPVOH-alkyl acrylate copolymer (Resin A) (e.g., at a ratio of 0/100).Without intending to be bound by theory, it is believed that when a filmdemonstrates an increase in swelling ratio value that is less than 60%of the swelling ratio value for a comparative film which is identicalbut for the second PVOH copolymer being the sole resin and the amount ofthat second PVOH copolymer in the comparative film being equal to thetotal amount of resins in the inventive water-soluble film (e.g., aratio of A/B of 0/100), the film is less likely to soften and droop(i.e., remains taut) when formed into pouches enclosing liquidcompositions.

FIGS. 3 and 4 are graphical representations of the data from Examples 5,7, 9, 11, 13, and 15, above. FIG. 3 shows the change in the DC residuevalues over time for films stored at ambient temperatures (3 a) and a38° C., 80% RH environment (3 b) for films made of PVOH resin blendsincluding a PVOH-acrylate copolymer and a PVOH-maleate copolymer. Thepercent acrylate of the blend is indicated in the legend, and thebalance of the resin is the maleate copolymer.

FIG. 4 is a graphical representation of the change in the filmdissolution at 10° C. as measured by MSTM-205 over time for films storedat ambient temperatures (4 a) and a 38° C., 80% RH environment (4 b) forfilms made of PVOH resin blends including a PVOH-acrylate copolymer anda PVOH-maleate copolymer. The percent acrylate of the blend is indicatedin the legend, and the balance of the resin is the maleate copolymer.

Examples 86-92: Single Resin Film Exposed to LLD

Films were prepared with Resin B, including plasticizers and othernon-resin components in the amounts and types described in Example 2.Aqueous compositions of the foregoing were cast and dried to form 76 μmthick film samples. The resulting films were exposed to liquid laundrydetergent two (LLD 2) as described herein. The films were tested for DCresidue values by the above methods prior to storing in contact with theLLD 2 and after storing in contact with the LLD 2 for 3, 6, or 12 weeksat ambient conditions (23° C., 35% RH) or a high stress 38° C., 80% RHenvironment. The average DC values are summarized in Table 18. In Table18, the pendant group (P) content for the film is provided on a molarbasis relative to the PVOH resins in the film (i.e., excluding theplasticizers and the other non-resin components thereof), and the Pvalue further indicates that the pendant group corresponds to a maleicanhydride comonomer unit (M).

TABLE 18 Resin and Film Data for Examples 31-36 Weeks EnvironmentExample Type Stored Conditions DC (%) P (mol. %) 86 B 0 23° C., 35% RH0.73* 8.00 (M) 87 B 3 23° C., 35% RH 1.78* 8.00 (M) 88 B 6 23° C., 35%RH 3.87* 8.00 (M) 89 B 12 23° C., 35% RH 2.97* 8.00 (M) 90 B 3 38° C.,80% RH 3.28* 8.00 (M) 91 B 6 38° C., 80% RH 1.11* 8.00 (M) 92 B 12 38°C., 80% RH 2.20* 8.00 (M)

In Table 18, residue values marked with an “*” satisfy the criteria forgood DC residue values, i.e., less than 35 wt. %. Table 18 demonstratesthat water-soluble films comprising a single PVOH resin comprising amaleic anhydride co-monomer can demonstrate good residue values.

Examples 93-99: Single Resin Film Exposed to LLD

Films were prepared with Resin A and non-resin components in the amountsand types described in Example 1. Films were formed and tested asdescribed for Examples 86 to 92. The average DC values are summarized inTable 19. In Table 19, the pendant group (P) content for the film isprovided on a molar basis relative to the PVOH resins in the film (i.e.,excluding the plasticizers and the other non-resin components thereof),and the P value further indicates that the pendant group corresponds toa methyl acrylate comonomer unit (A).

TABLE 19 Resin and Film Data for Examples 93-99 Weeks EnvironmentExample Type Stored Conditions DC (%) P (mol. %) 93 A 0 23° C., 35% RH11.43* 5.00 (A) 94 A 3 23° C., 35% RH 27.08* 5.00 (A) 95 A 6 23° C., 35%RH 25.20* 5.00 (A) 96 A 12 23° C., 35% RH 30.55* 5.00 (A) 97 A 3 38° C.,80% RH 30.59* 5.00 (A) 98 A 6 38° C., 80% RH 40.35 5.00 (A) 99 A 12 38°C., 80% RH 58.15 5.00 (A)

In Table 19, residue values marked with an “*” satisfy the DC residuecriteria as described in Examples 86 to 92. Table 19 demonstrates thatwater-soluble films comprising a single PVOH resin comprising a methylacrylate co-monomer can demonstrate poor residue values upon storage incontact with a liquid laundry detergent under high stress (e.g., 38° C.,80% RH) conditions.

Examples 100-106: Two-Resin Blend Film

Examples 100-106 represent water-soluble films which were formed, eachincluding a blend of the two copolymer Resins A and B. The films eachincluded 80 wt. % Resin A and 20 wt. % Resin B. The blend films includedthe two resins that made up 100% of the resin in the film, whileplasticizers and other non-resin components were present in the amountsand types as described for Example 1. Films were prepared and tested asdescribed in Examples 86 to 92. The average DC values are summarized inTable 20. In Table 20, the pendant group (P) content for the films isprovided on a molar basis relative to all of the polymeric resin in thefilm (i.e., including both resins present but excluding the plasticizersand the other non-resin components thereof), and the P values furtherindicate whether they correspond to a methyl acrylate comonomer unit (A)or a maleic anhydride comonomer unit (M).

TABLE 20 Resin and Film Data for Examples 100-106 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 100 80/20 023° C., 35% RH 3.86* 5.6 (A/M) 101 80/20 3 23° C., 35% RH 12.63* 5.6(A/M) 102 80/20 6 23° C., 35% RH 14.81* 5.6 (A/M) 103 80/20 12 23° C.,35% RH 15.30* 5.6 (A/M) 104 80/20 3 38° C., 80% RH 13.79* 5.6 (A/M) 10580/20 6 38° C., 80% RH 20.11* 5.6 (A/M) 106 80/20 12 38° C., 80% RH22.03* 5.6 (A/M)

In Table 20, residue values marked with an “*” satisfy the DC residuevalue criteria as described in Examples 86 to 92. As shown in Examples100-106, it unexpectedly has been found that certain water-soluble filmscontaining PVOH resin blends with about 80 wt. % a first PVOH copolymercomprising a first anionic monomer as described herein and about 20 wt.% of a second PVOH copolymer comprising a second anionic monomer asdescribed herein generally meet the criteria for acceptable residuevalues up to at least 12 weeks of storage at ambient conditions and upto at least 12 weeks of storage at 38° C., 80% RH conditions.

Examples 107-113: Two-Resin Blend Films

Examples 107 to 113 represent water-soluble films which were formed,each including a blend of the two copolymer Resins A and B. The filmseach included 60 wt. % Resin A and 40 wt. % Resin B. The blend filmsincluded the two resins that made up 100% of the resin in the film,while plasticizers and other non-resin components were present in theamounts and types as described for Example 1. Films were prepared andtested as described in Examples 86 to 92. The average DC values aresummarized in Table 21. In Table 21, the pendant group (P) content forthe film is provided on a molar basis relative to all of the polymericresin in the film (i.e., including both resins present but excluding theplasticizers and the other non-resin components thereof), and the Pvalues further indicate whether they correspond to a methyl acrylatecomonomer unit (A) or a maleic anhydride comonomer unit (M).

TABLE 21 Resin and Film Data for Examples 107-113 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 107 60/40 023° C., 35% RH 6.31* 6.2 (A/M) 108 60/40 3 23° C., 35% RH 10.07* 6.2(A/M) 109 60/40 6 23° C., 35% RH 7.88* 6.2 (A/M) 110 60/40 12 23° C.,35% RH 7.80* 6.2 (A/M) 111 60/40 3 38° C., 80% RH 10.74* 6.2 (A/M) 11260/40 6 38° C., 80% RH 13.14* 6.2 (A/M) 113 60/40 12 38° C., 80% RH7.48* 6.2 (A/M)

In Table 21, residue values marked with an “*” satisfy the DC residuevalue criteria as described in Examples 86 to 92. As shown in Examples107-113, it unexpectedly has been found that certain water-soluble filmscontaining PVOH resin blends with about 60 wt. % a first PVOH copolymercomprising a first anionic monomer as described herein and about 40 wt.% of a second PVOH copolymer comprising a second anionic monomer asdescribed herein generally meet the criteria for acceptable residuevalues up to at least 12 weeks of storage at ambient conditions and upto at least 12 weeks of storage at 38° C., 80% RH conditions.

Examples 114-120: Two-Resin Blend Films

Examples 114-120 represent water-soluble films which were formed, eachincluding a blend of the two copolymer Resins A and B. The films eachinclude 40 wt. % Resin A and 60 wt. % Resin B. The blend films includedthe two resins that made up 100% of the resin in the film, whileplasticizers and other non-resin components were present in the amountsand types as described for Example 1. Films were prepared as describedin Examples 86 to 92. The average DC values are summarized in Table 22.In Table 22, the pendant group (P) content for the film is provided on amolar basis relative to all of the polymeric resin in the film (i.e.,including both resins present but excluding the plasticizers and theother non-resin components thereof), and the P values further indicatewhether they correspond to a methyl acrylate comonomer unit (A) or amaleic anhydride comonomer unit (M).

TABLE 22 Resin and Film Data for Examples 114-120 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 114 40/60 023° C., 35% RH 3.96* 6.8 (A/M) 115 40/60 3 23° C., 35% RH 9.05* 6.8(A/M) 116 40/60 6 23° C., 35% RH 13.93* 6.8 (A/M) 117 40/60 12 23° C.,35% RH 12.96* 6.8 (A/M) 118 40/60 3 38° C., 80% RH 9.78* 6.8 (A/M) 11940/60 6 38° C., 80% RH 12.95* 6.8 (A/M) 120 40/60 12 38° C., 80% RH6.55* 6.8 (A/M)

In Table 22, residue values marked with an “*” satisfy the DC residuevalue criteria as described in Examples 86 to 92. As shown in Examples114-120, it unexpectedly has been found that certain water-soluble filmscontaining PVOH resin blends with about 40 wt. % a first PVOH copolymercomprising a first anionic monomer as described herein and about 60 wt.% of a second PVOH copolymer comprising a second anionic monomer asdescribed herein generally meet the criteria for acceptable residuevalues up to at least 12 weeks of storage at ambient conditions and upto at least 12 weeks of storage at 38° C., 80% RH conditions.

Examples 121-127: Two-Resin Blend Films

Examples 121-127 represent water-soluble films which were formed, eachincluding a blend of the two copolymer Resins A and B. The films eachincluded 20 wt. % Resin A and 80 wt. % Resin B. The blend films includedthe two resins that made up 100% of the resin in the film, whileplasticizers and other non-resin components were present in the amountsand types as described for Example 1. Films were prepared and tested asdescribed in Examples 86 to 92. The average DC values are summarized inTable 23. In Table 23, the pendant group (P) content for the film isprovided on a molar basis relative to all of the polymeric resin in thefilm (i.e., including both resins present but excluding the plasticizersand the other non-resin components thereof), and the P values furtherindicate whether they correspond to a methyl acrylate comonomer unit (A)or a maleic anhydride comonomer unit (M).

TABLE 23 Resin and Film Data for Examples 121-127 Type (Ratio of WeeksEnvironment Example A/B) Stored Conditions DC (%) P (mol. %) 121 20/80 023° C., 35% RH 3.09* 7.4 (A/M) 122 20/80 3 23° C., 35% RH 12.13* 7.4(A/M) 123 20/80 6 23° C., 35% RH 13.02* 7.4 (A/M) 124 20/80 12 23° C.,35% RH 9.67* 7.4 (A/M) 125 20/80 3 38° C., 80% RH 12.82* 7.4 (A/M) 12620/80 6 38° C., 80% RH 11.75* 7.4 (A/M) 127 20/80 12 38° C., 80% RH7.35* 7.4 (A/M)

In Table 23, residue values marked with an “*” satisfy the DC residuevalue criteria described in Examples 86 to 92. As shown in Examples121-127, it unexpectedly has been found that certain water-soluble filmscontaining PVOH resin blends with about 20 wt. % a first PVOH copolymercomprising a first anionic monomer as described herein and about 80 wt.% of a second PVOH copolymer comprising a second anionic monomer asdescribed herein generally meet the criteria for acceptable residuevalues up to at least 12 weeks of storage at ambient conditions and upto at least 12 weeks of storage at 38° C., 80% RH conditions.

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the invention may be apparent to thosehaving ordinary skill in the art.

All patents, publications and references cited herein are hereby fullyincorporated by reference. In case of conflict between the presentdisclosure and incorporated patents, publications and references, thepresent disclosure should control.

1. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resinblend comprising: a first PVOH copolymer comprising a first anionicmonomer unit, the first anionic monomer unit selected from the groupconsisting of alkyl acrylates, alkyl alkacrylates, hydrolyzed alkalimetal salts of the foregoing, and combinations of the foregoing; and asecond PVOH copolymer comprising a second anionic monomer unit; whereinthe first PVOH copolymer is provided in an amount in a range of about 10wt. % to about 40 wt. %, based on the total weight of the PVOH resinblend, and the first anionic monomer unit is different from the secondanionic monomer unit.
 2. The water-soluble film of claim 1, wherein thesecond anionic monomer is selected from the group consisting of vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleicanhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, fumaricanhydride, itaconic acid, monoalkyl itaconate, dialkyl itaconate,itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkylcitraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate,dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkylglutaconate, dialkyl glutaconate, glutaconic anhydride, alkali metalsalts of the foregoing, esters of the foregoing, and combinations of theforegoing.
 3. The water-soluble film of claim 1, wherein the first PVOHcopolymer has a first level of pendant groups (a1); and the second PVOHcopolymer has a second level of pendant groups (a2); wherein thedifference between a1 and a2 is in a range of about 2 mol % to about 10mol %.
 4. The water-soluble film of claim 1, wherein the first PVOHcopolymer is present in an amount in a range of about 20 wt. % to about40 wt. % of total weight of the PVOH resin blend.
 5. The water-solublefilm of claim 1, wherein the second anionic monomer comprises a monomerselected from one or more of maleic anhydride and an alkali metal saltof maleic anhydride.
 6. The water-soluble film of claim 1, wherein thesecond PVOH copolymer is present in an amount in a range of about 60 wt.% to about 90 wt. % of total PVOH polymer in the film.
 7. Thewater-soluble film of claim 1, wherein the PVOH copolymer comprisesfirst pendant groups and the second PVOH copolymer comprises secondpendant groups, and the first and second pendant groups are togetherpresent in a combined amount in a range of about 2 mol % to 15 mol %. 8.The water-soluble film of claim 1, wherein the first PVOH copolymer isan alkyl acrylate copolymer having a first level of anionic monomerincorporation (b₁), and the second PVOH copolymer is a maleic anhydridecopolymer having a second level of anionic monomer incorporation (b₂),wherein the difference between b₁ and b₂ is in a range of about 0.2 to 2mol %.
 9. The water-soluble film of claim 1, wherein the first PVOHcopolymer has a 4% solution viscosity at 20° C. in a range of about 4 cPto about 24 cP.
 10. The water-soluble film of claim 1, wherein thesecond PVOH copolymer has a 4% solution viscosity at 20° C. in a rangeof about 12 cP to about 30 cP.
 11. The water-soluble film of claim 1,wherein the water-soluble film has a residue value of about 35 wt. % orless as measured by the Dissolution Chamber Test.
 12. The water-solublefilm of claim 1, wherein the water-soluble film has a crystallinity ofat least 15%.
 13. The water soluble film of claim 1 wherein the PVOHresin blend consists essentially of the first PVOH copolymer and thesecond PVOH copolymer.
 14. The water-soluble film of claim 1, whereinthe water-soluble film further comprises at least a third water-solublepolymer which is other than a PVOH polymer.
 15. The water-soluble filmof claim 14, wherein the third water-soluble polymer is selected fromone or more of a polyethyleneimine, a polyvinyl pyrrolidone, apolyalkylene oxide, a polyacrylamide, a cellulose ether, a celluloseester, a cellulose amide, a polyvinyl acetate, a polyamide, a gelatine,a methylcellulose, a carboxymethylcellulose, a carboxymethylcellulosesalt, a dextrin, an ethylcellulose, a hydroxyethyl cellulose, ahydroxypropyl methylcellulose, a maltodextrin, a starch, a modifiedstarch, guar gum, gum Acacia, xanthan gum, carrageenan, a polyacrylate,a polyacrylate salt, and a copolymer of any of the foregoing.
 16. Thewater-soluble film of claim 1, wherein the first PVOH copolymer and thesecond PVOH copolymer each independently have a degree of hydrolysis ina range of about 75% to about 99%.
 17. The water-soluble film of claim1, wherein the water-soluble film further comprises an auxiliary agentselected from one or more of a plasticizer, a plasticizercompatibilizer, a lubricant, a release agent, a filler, an extender, across-linking agent, an antiblocking agent, an antioxidant, adetackifying agent, an antifoam, a nanoparticle, a bleaching agent, anda surfactant.
 18. The water-soluble film of claim 1, further comprisingone or more plasticizers in an amount of 30 phr or greater.
 19. Thewater-soluble film of claim 1, further comprising one or moreplasticizers in an amount of less than 30 phr.
 20. The water-solublefilm of claim 1, comprising a first plasticizer having a molecularweight of 92 g/mol or greater and a second plasticizer having amolecular weight of 150 g/mol or greater.
 21. The water-soluble film ofclaim 20, further comprising a third plasticizer.
 22. The water-solublefilm of claim 1, further comprising a filler in an amount of at least 2phr.
 23. The water-soluble film of claim 22, wherein the fillercomprises a bulking agent, an antiblocking agent, or a combinationthereof.
 24. The water-soluble film of claim 3, wherein: the first PVOHcopolymer comprises an alkyl acrylate monomer unit; the first PVOHcopolymer is present in an amount in a range of about 10 wt % to about40 wt % of the total weight of the PVOH resin blend; the second PVOHcopolymer comprises a second anionic monomer unit selected from one ormore of a maleic anhydride and an alkali metal salt of maleic anhydride;the second PVOH copolymer is present in an amount in a range of about 60wt % to about 90 wt % of the total weight of the PVOH resin blend;wherein the difference between a₁ and a₂ is in a range of about 2 mol %to about 6 mol %; a₁ is in a range of about 2 mol % to about 6 mol %; a₂is in a range of about 7 mol % to about 9 mol %; and the first pendantgroup and the second pendant group are together present in a combinedamount in a range of about 2 mol % to 15 mol %.
 25. An articlecomprising: a water-soluble film of claim 1 in the form of a pouchdefining an interior pouch volume.
 26. The article of claim 25, furthercomprising a composition contained in the interior pouch volume.
 27. Thearticle of claim 26, wherein the composition is a liquid composition.28. The article of claim 27, wherein the liquid composition is a liquiddetergent.
 29. The article of claim 27, wherein the liquid compositioncomprises a low molecular weight polyol.
 30. The article of claim 26,wherein the composition contained in the interior pouch volume is aliquid and the article has a delayed release time of at least 30 secondsas measured by the Liquid Release Test.